Strigolactam derivatives as plant growth regulating compounds

ABSTRACT

The present invention relates to novel strigolactam derivatives of formula (I), to processes and intermediates for preparing them, to plant growth regulator compositions comprising them and to methods of using them for controlling the growth of plants and/or promoting the germination of seeds.

The present invention relates to novel strigolactam derivatives, toprocesses and intermediates for preparing them, to plant growthregulator compositions comprising them and to methods of using them forcontrolling the growth of plants and/or promoting the germination ofseeds.

Strigolactone derivatives are phytohormones with plant growth regulationand seed germination properties; they have been described, for example,in WO2009/138655, WO2010/125065, WO05/077177, WO06/098626, and AnnualReview of Phytopathology (2010), 48 p. 93-117. Strigolactonederivatives, like the synthetic analogue GR24, are known to have effecton the germination of parasitic weeds, such as Orobanche species. It iswell established in the art that testing for germination of Orobancheseeds is a useful test to identify strigolactone analogues (for example,see Plant and Cell Physiology (2010), 51(7) p. 1095; and Organic &Biomolecular Chemistry (2009), 7(17), p. 3413).

It has now surprisingly been found that certain strigolactam derivativeshave properties analogous to strigolactone. These were also found tohave crop enhancement properties.

According to the present invention, there is provided a compound ofFormula (I)

wherein

W is O or S;

R2 and R3 are independently hydrogen, or C₁-C₃ alkyl;R4 and R5 are independently hydrogen, halogen, nitro, cyano, C₁-C₃alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, hydroxyl, —OC(O)R9, amine, N—C₁-C₃ alkyl amine, or N,N-di-C₁-C₃ alkyl amine;R9 is hydrogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₁-C₆ haloalkyl;R6 and R7 are independently hydrogen, C₁-C₃ alkyl, hydroxyl, halogen orC₁-C₃ alkoxy;R8 is hydrogen, nitro, cyano, C₁-C₆ alkyl, C₁-C₆ haloalkyl, halogen,C₁-C₈ alkylthio, C₁-C₈ haloalkylthio, C₁-C₈ alkylsulfinyl, N— C₁-C₆alkyl amine, N,N-di-C₁-C₆ alkyl amine, C₁-C₈ haloalkylsulfinyl, C₁-C₈alkylsulfonyl, or C₁-C₈ haloalkylsulfonyl;R1 is hydrogen, C₁-C₆ alkoxy, hydroxyl, amine, N— C₁-C₆ alkyl amine,N,N-di-C₁-C₆ alkyl amine, C₁-C₆ alkyl optionally substituted by one tofive R10, C₁-C₈ alkylcarbonyl, C₁-C₈ alkoxycarbonyl, aryl optionallysubstituted by one to five R10, heteroaryl optionally substituted by oneto five R10, heterocyclyl optionally substituted by one to five R10, orbenzyl optionally substituted by one to five R10;R10 is hydrogen, cyano, nitro, halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆haloalkyl, C₂-C₆ alkenyl, or C₂-C₆ alkynyl;A₁, A₂, A₃ and A₄ are each independently C—X, C—Y or nitrogen, whereineach X or Y may be the same or different, and provided that no more thantwo of A₁, A₂, A₃ and A₄ are nitrogen and that at least one of A₁, A₂,A₃ and A₄ is C—X;Y is hydrogen, halogen, cyano, hydroxyl, —OC(O)R9, C₁-C₆ alkoxy, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₁-C₃ hydroxyalkyl, nitro, amine, N— C₁-C₆ alkylamine, N,N-di-C₁-C₆ alkyl amine, or NHC(O)R9;X is C₂-C₈ alkenyl optionally substituted by one to five R11, C₂-C₈alkynyl optionally substituted by one to five R11, C₃-C₇ cycloalkyl,C₃-C₁₀ cycloalkyl substituted by one to five R12, C₁-C₈alkylcarbonyl,C₁-C₈ alkoxycarbonyl, N— C₁-C₆ alkyl aminocarbonyl, N,N-di-C₁-C₆ alkylaminocarbonyl, aryl optionally substituted by one to five R13, orheteroaryl optionally substituted by one to five R13;each R11 is independently halogen, cyano, nitro, hydroxy,C₁-C₈haloalkyl, C₁-C₈alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ alkylthio, C₁-C₈haloalkylthio, C₁-C₈ alkylsulfinyl, N— C₁-C₆ alkyl amine, N,N-di-C₁-C₆alkyl amine, C₁-C₈haloalkylsulfinyl, C₁-C₈ alkylsulfonyl, C₁-C₈haloalkylsulfonyl, C₁-C₈alkylcarbonyl, C₁-C₈alkoxycarbonyl; or aryloptionally substituted by one to five halogen, C₁-C₃ alkyl, C₁-C₃alkoxy; or heteroaryl optionally substituted by one to five halogen,C₁-C₃ alkyl, C₁-C₃ alkoxy; andeach R12 and R13 are independently halogen, cyano, nitro, hydroxy, C₁-C₈alkyl, C₁-C₈alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ alkylthio, C₁-C₈haloalkylthio, C₁-C₈ alkylsulfinyl, N— C₁-C₆ alkyl amine, N,N-di-C₁-C₆alkyl amine, C₁-C₈ haloalkylsulfinyl, C₁-C₈ alkylsulfonyl, C₁-C₈haloalkylsulfonyl, C₁-C₈alkylcarbonyl, C₁-C₈ alkoxycarbonyl, or phenyl;or salts or N-oxides thereof.

The compounds of Formula (I) may exist in different geometric or opticalisomers (diastereoisomers and enantiomers) or tautomeric forms. Thisinvention covers all such isomers and tautomers and mixtures thereof inall proportions as well as isotopic forms such as deuterated compounds.The invention also covers all salts, N-oxides, and metalloidic complexesof the compounds of Formula (I).

Each alkyl moiety either alone or as part of a larger group (such asalkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl) is a straight or branched chain and is, forexample, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or neo-pentyl. Thealkyl groups are preferably C₁ to C₆ alkyl groups, more preferably C₁-C₄and most preferably C₁-C₃ alkyl groups.

Each alkenyl moiety either alone or as part of a larger group (such asalkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl) is having at least one carbon-carbon double bondand is, for example, vinyl, allyl. The alkenyl groups are preferably C₂to C₆ alkenyl groups, more preferably C₂-C₄ alkenyl groups.

The term “alkenyl”, as used herein, unless otherwise indicated, includesalkyl moieties having at least one carbon-carbon double bond whereinalkyl is as defined above

Each alkynyl moiety either alone or as part of a larger group (such asalkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl) is having at least one carbon-carbon triple bondand is, for example, ethynyl, propargyl. The alkynyl groups arepreferably C₂ to C₆ alkynyl groups, more preferably C₂-C₄ alkynylgroups. The term “alkynyl”, as used herein, unless otherwise indicated,includes alkyl moieties having at least one carbon-carbon triple bondwherein alkyl is as defined above.

Halogen is fluorine, chlorine, bromine or iodine.

Haloalkyl groups (either alone or as part of a larger group, such ashaloalkoxy or haloalkylthio) are alkyl groups which are substituted withone or more of the same or different halogen atoms and are, for example,—CF₃, —CF₂Cl, —CH₂CF₃ or —CH₂CHF₂.

Hydroxyalkyl groups are alkyl groups which are substituted with one ormore hydroxyl group and are, for example, —CH₂OH, —CH₂CH₂OH or—CH(OH)CH₃.

In the context of the present specification the term “aryl” refers to aring system which may be mono-, bi- or tricyclic. Examples of such ringsinclude phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. Apreferred aryl group is phenyl.

Unless otherwise indicated, alkenyl and alkynyl, on their own or as partof another substituent, may be straight or branched chain and maypreferably contain 2 to 6 carbon atoms, preferably 2 to 4, morepreferably 2 to 3, and where appropriate, may be in either the (E)- or(Z)-configuration. Examples include vinyl, allyl ethynyl and propargyl.

Unless otherwise indicated, cycloalkyl may be mono- or bi-cyclic, may beoptionally substituted by one or more C₁-C₆ alkyl groups, and preferablycontain 3 to 7 carbon atoms, more preferably 3 to 6 carbon atoms.Examples of cycloalkyl include cyclopropyl, 1-methylcyclopropyl,2-methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term “heteroaryl” refers to an aromatic ring system containing atleast one heteroatom and consisting either of a single ring or of two ormore fused rings. Preferably, single rings will contain up to three andbicyclic systems up to four heteroatoms which will preferably be chosenfrom nitrogen, oxygen and sulfur. Examples of such groups includepyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, furanyl, thiophenyl,oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl,thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl.

The term “heterocyclyl” is defined to include heteroaryl, saturatedanalogs, and in addition their unsaturated or partially unsaturatedanalogues such as 4,5,6,7-tetrahydro-benzothiophenyl, 9H-fluorenyl,3,4-dihydro-2H-benzo-1,4-dioxepinyl, 2,3-dihydro-benzo-furanyl,piperidinyl, 1,3-dioxolanyl, 1,3-dioxanyl, 4,5-dihydro-isoxazolyl,tetrahydrofuranyl and morpholinyl. In addition, the term “heterocyclyl”is defined to include “heterocycloalkyl” defined to be a non-aromaticmonocyclic or polycyclic ring comprising carbon and hydrogen atoms andat least one heteroatom, preferably, 1 to 4 heteroatoms selected fromnitrogen, oxygen, and sulfur such as oxirane or thietane.

Preferred values of W, R2, R3, R4, R5, R6, R7, R8, R1, R10, A₁, A₂, A₃,A₄ and X are, in any combination, as set out below.

W is preferably oxygen.R2 is preferably hydrogen, methyl, or ethyl; most preferably R2 ishydrogen.R3 is preferably hydrogen, methyl, or ethyl; most preferably R3 ishydrogen.R4 is preferably hydrogen, hydroxyl, methyl, or ethyl; most preferablyR4 is hydrogen or hydroxyl.R5 is preferably hydrogen, hydroxyl, methyl, or ethyl; most preferablyR5 is hydrogen or hydroxyl.R6 is preferably hydrogen, methyl, or ethyl; most preferably R6 ismethyl.R7 is preferably hydrogen, methyl, methoxy, chloride or ethyl; mostpreferably R7 is hydrogen.R8 is preferably hydrogen, methyl, or ethyl; most preferably R8 ishydrogen.R1 is preferably hydrogen, C₁-C₆ alkoxy, C₁-C₆ alkyl optionallysubstituted by one to five R10, C₁-C₈ alkylcarbonyl, C₁-C₈alkoxycarbonyl, aryl optionally substituted by one to five R10,heteroaryl optionally substituted by one to five R10, heterocyclyloptionally substituted by one to five R10, or benzyl optionallysubstituted by one to five R10; more preferably R1 is hydrogen, C₁-C₆alkoxy, C₁-C₆ alkyl optionally substituted by one to five R10, C₁-C₈alkylcarbonyl, C₁-C₈ alkoxycarbonyl, or benzyl optionally substituted byone to five R10; most preferably R1 is hydrogen, methyl, ethyl, phenyl,benzyl, acetate, methoxycarbonyl, or tertbutoxycarbonyl.R10 is independently hydrogen, cyano, nitro, halogen, C₁-C₆ alkyl, C₁-C₆alkoxy, C₁-C₆ haloalkyl; most preferably R10 is hydrogen, cyano, nitro,chloride, bromine, fluorine, methyl, methoxy or trifluoromethyl.Preferably A₁ is C—X and A₂, A₃, A₄ are CY. More preferably A₁ is C—Xand A₂, A₃, A₄ are C—H.Preferably A₂ is C—X and A₁, A₃, A₄ are CY. More preferably A₂ is C—Xand A₁, A₃, A₄ are C—H.Preferably A₃ is C—X and A₁, A₂, A₄ are CY. More preferably A₃ is C—Xand A₁, A₂, A₄ are C—H.Preferably A₄ is C—X and A₁, A₂, A₃ are CY. More preferably A₄ is C—Xand A₁, A₂, A₃ are C—H.Preferably, Y is hydrogen, hydroxyl, halogen, cyano, methyl,hydroxymethyl, trifluoromethyl or methoxy. More preferably, Y ishydrogen, hydroxyl, methyl, trifluoromethyl or methoxy. Even morepreferably, Y is hydrogen, methyl, hydroxyl or methoxy. Most preferably,Y is hydrogen.Preferably, X is vinyl, 1-propenyl, allyl, propargyl, cyclopropane,cyclobutane, cyclopentane, ethynyl, benzene ethynyl, methyl ethynyl,phenyl optionally substituted by one to five R13, pyridyl optionallysubstituted by one to five R13, furanyl optionally substituted by one tofive R13, thiophenyl optionally substituted by one to five R13, thiazoyloptionally substituted by one to five R13, methoxycarbonyl,hydroxycarbonyl, methylaminocarbonyl, or dimethylaminocarbonyl. Morepreferably, X is vinyl, 1-propenyl, allyl, propargyl, cyclopropane,ethynyl, phenyl, pyridyl, furanyl, thiophenyl, thiazoyl,methoxycarbonyl, hydroxycarbonyl, methylaminocarbonyl, ordimethylaminocarbonyl.Preferably, R12 and R13 are independently halogen, cyano, nitro,hydroxy, methoxy, or methyl.

In a preferred embodiment the compound is of Formula (II).

wherein

W is O or S;

R2 and R3 are independently hydrogen, or C₁-C₃ alkyl;R4 and R5 are independently hydrogen, halogen, nitro, cyano, C₁-C₃alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, hydroxyl, —OC(O)R9, amine, N—C₁-C₃ alkyl amine, or N,N-di-C₁-C₃ alkyl amine;R9 is hydrogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₁-C₆ haloalkyl;R8 is hydrogen, nitro, cyano, C₁-C₆ alkyl, C₁-C₆ haloalkyl, halogen,C₁-C₈ alkylthio, C₁-C₈ haloalkylthio, C₁-C₈alkylsulfinyl, N—C₁-C₆ alkylamine, N,N-di-C₁-C₆ alkyl amine, C₁-C₈ haloalkylsulfinyl,C₁-C₈alkylsulfonyl, or C₁-C₈haloalkylsulfonyl;R1 is hydrogen, C₁-C₆ alkoxy, hydroxyl, amine, N—C₁-C₆ alkyl amine,N,N-di-C₁-C₆ alkyl amine, C₁-C₆ alkyl optionally substituted by one tofive R10, C₁-C₈ alkylcarbonyl, C₁-C₈ alkoxycarbonyl, aryl optionallysubstituted by one to five R10, heteroaryl optionally substituted by oneto five R10, or benzyl optionally substituted by one to five R10;R10 is hydrogen, cyano, nitro, halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆haloalkyl, C₂-C₆ alkenyl, or C₂-C₆ alkynyl;A₁, A₂, A₃ and A₄ are each independently C—X, C—Y or nitrogen, whereineach X or Y may be the same or different, and provided that no more thantwo of A₁, A₂, A₃ and A₄ are nitrogen and that at least one of A₁, A₂,A₃ and A₄ is C—X;Y is hydrogen, halogen, cyano, hydroxyl, —OC(O)R9, C₁-C₆ alkoxy, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₁-C₃ hydroxyalkyl, nitro, amine, N—C₁-C₆ alkylamine, N,N-di-C₁-C₆ alkyl amine, or NHC(O)R9;X is C₂-C₈ alkenyl optionally substituted by one to five R11, C₂-C₈alkynyl optionally substituted by one to five R11, C₃-C₇ cycloalkyl,C₃-C₁₀ cycloalkyl substituted by one to five R12, C₁-C₈alkylcarbonyl,C₁-C₈ alkoxycarbonyl, N—C₁-C₆ alkyl aminocarbonyl, N,N-di-C₁-C₆ alkylaminocarbonyl, aryl optionally substituted by one to five R13, orheteroaryl optionally substituted by one to five R13;each R11 is independently halogen, cyano, nitro, hydroxy, C₁-C₈haloalkyl, C₁-C₈alkoxy-, C₁-C₈ haloalkoxy, C₁-C₈ alkylthio, C₁-C₈haloalkylthio, C₁-C₈ alkylsulfinyl, N—C₁-C₆ alkyl amine, N,N-di-C₁-C₆alkyl amine, C₁-C₈ haloalkylsulfinyl, C₁-C₈ alkylsulfonyl, C₁-C₈haloalkylsulfonyl, C₁-C₈alkylcarbonyl, C₁-C₈ alkoxycarbonyl; or aryloptionally substituted by one to five halogen, C1-C3 alkyl, C1-C3alkoxy; or heteroaryl optionally substituted by one to five halogen,C1-C3 alkyl, C1-C3 alkoxy; andeach R12 and R13 are independently halogen, cyano, nitro, hydroxy, C₁-C₈alkyl-, C₁-C₈ alkoxy-, C₁-C₈haloalkoxy, C₁-C₈ alkylthio,C₁-C₈haloalkylthio, C₁-C₈ alkylsulfinyl, N—C₁-C₆ alkyl amine,N,N-di-C₁-C₆ alkyl amine, C₁-C₈ haloalkylsulfinyl, C₁-C₈ alkylsulfonyl,C₁-C₈ haloalkylsulfonyl, C₁-C₈alkylcarbonyl, C₁-C₈ alkoxycarbonyl, orphenyl;or salts or N-oxides thereof.

The preferences for A₁, A₂, A₃, A₄, R1, R2, R3, R4, R5, R8 and W are thesame as the preferences set out for the corresponding substituents ofthe compounds of the Formula (I).

Table 1 below includes examples of compounds of Formula (I) wherein W isO, R2 is H, R3 is H, R6 is methyl, R7 is H, R8 is H and A₁, A₂, A₃, A₄,R1, R4 and R5 are as defined.

TABLE 1 (I)

Com- pound R1 R4 R5 A₁ A₂ A₃ A₄ 1.00 H H H C—CCH C—H C—H C—H 1.01 H OH HC—CCH C—H C—H C—H 1.02 CH₃ H H C—CCH C—H C—H C—H 1.03 CH₃ OH H C—CCH C—HC—H C—H 1.04 H H H C—H C—CCH C—H C—H 1.05 H OH H C—H C—CCH C—H C—H 1.06CH₃ H H C—H C—CCH C—H C—H 1.07 CH₃ OH H C—H C—CCH C—H C—H 1.08 H H H C—HC—H C—CCH C—H 1.09 H OH H C—H C—H C—CCH C—H 1.10 CH₃ H H C—H C—H C—CCHC—H 1.11 CH₃ OH H C—H C—H C—CCH C—H 1.12 H H H C—H C—H C—H C—CCH 1.13 HOH H C—H C—H C—H C—CCH 1.14 CH₃ H H C—H C—H C—H C—CCH 1.15 CH₃ OH H C—HC—H C—H C—CCH 1.16 H H H C—CHCH₂ C—H C—H C—H 1.17 H OH H C—CHCH₂ C—H C—HC—H 1.18 CH₃ H H C—CHCH₂ C—H C—H C—H 1.19 CH₃ OH H C—CHCH₂ C—H C—H C—H1.20 H H H C—H C—CHCH₂ C—H C—H 1.21 H OH H C—H C—CHCH₂ C—H C—H 1.22 CH₃H H C—H C—CHCH₂ C—H C—H 1.23 CH₃ OH H C—H C—CHCH₂ C—H C—H 1.24 H H H C—HC—H C—CHCH₂ C—H 1.25 H OH H C—H C—H C—CHCH₂ C—H 1.26 CH₃ H H C—H C—HC—CHCH₂ C—H 1.27 CH₃ OH H C—H C—H C—CHCH₂ C—H 1.28 H H H C—H C—H C—HC—CHCH₂ 1.29 H OH H C—H C—H C—H C—CHCH₂ 1.30 CH₃ H H C—H C—H C—H C—CHCH₂1.31 CH₃ OH H C—H C—H C—H C—CHCH₂ 1.32 H H H C—CH₂CHCH₂ C—H C—H C—H 1.33H OH H C—CH₂CHCH₂ C—H C—H C—H 1.34 CH₃ H H C—CH₂CHCH₂ C—H C—H C—H 1.35CH₃ OH H C—CH₂CHCH₂ C—H C—H C—H 1.36 H H H C—H C—CH₂CHCH₂ C—H C—H 1.37 HOH H C—H C—CH₂CHCH₂ C—H C—H 1.38 CH₃ H H C—H C—CH₂CHCH₂ C—H C—H 1.39 CH₃OH H C—H C—CH₂CHCH₂ C—H C—H 1.40 H H H C—H C—H C—CH₂CHCH₂ C—H 1.41 H OHH C—H C—H C—CH₂CHCH₂ C—H 1.42 CH₃ H H C—H C—H C—CH₂CHCH₂ C—H 1.43 CH₃ OHH C—H C—H C—CH₂CHCH₂ C—H 1.44 H H H C—H C—H C—H C—CH₂CHCH₂ 1.45 H OH HC—H C—H C—H C—CH₂CHCH₂ 1.46 CH₃ H H C—H C—H C—H C—CH₂CHCH₂ 1.47 CH₃ OH HC—H C—H C—H C—CH₂CHCH₂ 1.48 H H H C—CCCH₃ C—H C—H C—H 1.49 H OH HC—CCCH₃ C—H C—H C—H 1.50 CH₃ H H C—CCCH₃ C—H C—H C—H 1.51 CH₃ OH HC—CCCH₃ C—H C—H C—H 1.52 H H H C—H C—CCCH₃ C—H C—H 1.53 H OH H C—HC—CCCH₃ C—H C—H 1.54 CH₃ H H C—H C—CCCH₃ C—H C—H 1.55 CH₃ OH H C—HC—CCCH₃ C—H C—H 1.56 H H H C—H C—H C—CCCH₃ C—H 1.57 H OH H C—H C—HC—CCCH₃ C—H 1.58 CH₃ H H C—H C—H C—CCCH₃ C—H 1.59 CH₃ OH H C—H C—HC—CCCH₃ C—H 1.60 H H H C—H C—H C—H C—CCCH₃ 1.61 H OH H C—H C—H C—HC—CCCH₃ 1.62 CH₃ H H C—H C—H C—H C—CCCH₃ 1.63 CH₃ OH H C—H C—H C—HC—CCCH₃ 1.64 H H H C—Ph C—H C—H C—H 1.65 H OH H C—Ph C—H C—H C—H 1.66CH₃ H H C—Ph C—H C—H C—H 1.67 CH₃ OH H C—Ph C—H C—H C—H 1.68 H H H C—HC—Ph C—H C—H 1.69 H OH H C—H C—Ph C—H C—H 1.70 CH₃ H H C—H C—Ph C—H C—H1.71 CH₃ OH H C—H C—Ph C—H C—H 1.72 H H H C—H C—H C—Ph C—H 1.73 H OH HC—H C—H C—Ph C—H 1.74 CH₃ H H C—H C—H C—Ph C—H 1.75 CH₃ OH H C—H C—HC—Ph C—H 1.76 H H H C—H C—H C—H C—Ph 1.77 H OH H C—H C—H C—H C—Ph 1.78CH₃ H H C—H C—H C—H C—Ph 1.79 CH₃ OH H C—H C—H C—H C—Ph 1.80 H H HC—CH(CH₂)₂ C—H C—H C—H 1.81 H OH H C—CH(CH₂)₂ C—H C—H C—H 1.82 CH₃ H HC—CH(CH₂)₂ C—H C—H C—H 1.83 CH₃ OH H C—CH(CH₂)₂ C—H C—H C—H 1.84 H H HC—H C—CH(CH₂)₂ C—H C—H 1.85 H OH H C—H C—CH(CH₂)₂ C—H C—H 1.86 CH₃ H HC—H C—CH(CH₂)₂ C—H C—H 1.87 CH₃ OH H C—H C—CH(CH₂)₂ C—H C—H 1.88 H H HC—H C—H C—CH(CH₂)₂ C—H 1.89 H OH H C—H C—H C—CH(CH₂)₂ C—H 1.90 CH₃ H HC—H C—H C—CH(CH₂)₂ C—H 1.91 CH₃ OH H C—H C—H C—CH(CH₂)₂ C—H 1.92 H H HC—H C—H C—H C—CH(CH₂)₂ 1.93 H OH H C—H C—H C—H C—CH(CH₂)₂ 1.94 CH₃ H HC—H C—H C—H C—CH(CH₂)₂ 1.95 CH₃ OH H C—H C—H C—H C—CH(CH₂)₂ 1.96 H H H3-pyridyl C—H C—H C—H 1.97 H OH H 3-pyridyl C—H C—H C—H 1.98 CH₃ H H3-pyridyl C—H C—H C—H 1.99 CH₃ OH H 3-pyridyl C—H C—H C—H 1.100 H H HC—H 3-pyridyl C—H C—H 1.101 H OH H C—H 3-pyridyl C—H C—H 1.102 CH₃ H HC—H 3-pyridyl C—H C—H 1.103 CH₃ OH H C—H 3-pyridyl C—H C—H 1.104 H H HC—H C—H 3-pyridyl C—H 1.105 H OH H C—H C—H 3-pyridyl C—H 1.106 CH₃ H HC—H C—H 3-pyridyl C—H 1.107 CH₃ OH H C—H C—H 3-pyridyl C—H 1.108 H H HC—H C—H C—H 3-pyridyl 1.109 H OH H C—H C—H C—H 3-pyridyl 1.110 CH₃ H HC—H C—H C—H 3-pyridyl 1.111 CH₃ OH H C—H C—H C—H 3-pyridyl 1.112 H H H2-pyridyl C—H C—H C—H 1.113 H OH H 2-pyridyl C—H C—H C—H 1.114 CH₃ H H2-pyridyl C—H C—H C—H 1.115 CH₃ OH H 2-pyridyl C—H C—H C—H 1.116 H H HC—H 2-pyridyl C—H C—H 1.117 H OH H C—H 2-pyridyl C—H C—H 1.118 CH₃ H HC—H 2-pyridyl C—H C—H 1.119 CH₃ OH H C—H 2-pyridyl C—H C—H 1.120 H H HC—H C—H 2-pyridyl C—H 1.121 H OH H C—H C—H 2-pyridyl C—H 1.122 CH₃ H HC—H C—H 2-pyridyl C—H 1.123 CH₃ OH H C—H C—H 2-pyridyl C—H 1.124 H H HC—H C—H C—H 2-pyridyl 1.125 H OH H C—H C—H C—H 2-pyridyl 1.126 CH₃ H HC—H C—H C—H 2-pyridyl 1.127 CH₃ OH H C—H C—H C—H 2-pyridyl 1.128 H H HC—CO₂Me C—H C—H C—H 1.129 H OH H C—CO₂Me C—H C—H C—H 1.130 CH₃ H HC—CO₂Me C—H C—H C—H 1.131 CH₃ OH H C—CO₂Me C—H C—H C—H 1.132 H H H C—HC—CO₂Me C—H C—H 1.133 H OH H C—H C—CO₂Me C—H C—H 1.134 CH₃ H H C—HC—CO₂Me C—H C—H 1.135 CH₃ OH H C—H C—CO₂Me C—H C—H 1.136 H H H C—H C—HC—CO₂Me C—H 1.137 H OH H C—H C—H C—CO₂Me C—H 1.138 CH₃ H H C—H C—HC—CO₂Me C—H 1.139 CH₃ OH H C—H C—H C—CO₂Me C—H 1.140 H H H C—H C—H C—HC—CO₂Me 1.141 H OH H C—H C—H C—H C—CO₂Me 1.142 CH₃ H H C—H C—H C—HC—CO₂Me 1.143 CH₃ OH H C—H C—H C—H C—CO₂MeTable 2 below includes examples of compounds of Formula (II) wherein Wis O, R2 is H, R3 is H, R8 is H and A₁, A₂, A₃, A₄, R1, R4 and R5 are asdefined.

TABLE 2 (II)

Com- pound R1 R4 R5 A₁ A₂ A₃ A₄ 2.00 H H H C—CCH C—H C—H C—H 2.01 H OH HC—CCH C—H C—H C—H 2.02 CH₃ H H C—CCH C—H C—H C—H 2.03 CH₃ OH H C—CCH C—HC—H C—H 2.04 H H H C—H C—CCH C—H C—H 2.05 H OH H C—H C—CCH C—H C—H 2.06CH₃ H H C—H C—CCH C—H C—H 2.07 CH₃ OH H C—H C—CCH C—H C—H 2.08 H H H C—HC—H C—CCH C—H 2.09 H OH H C—H C—H C—CCH C—H 2.10 CH₃ H H C—H C—H C—CCHC—H 2.11 CH₃ OH H C—H C—H C—CCH C—H 2.12 H H H C—H C—H C—H C—CCH 2.13 HOH H C—H C—H C—H C—CCH 2.14 CH₃ H H C—H C—H C—H C—CCH 2.15 CH₃ OH H C—HC—H C—H C—CCH 2.16 H H H C—CHCH₂ C—H C—H C—H 2.17 H OH H C—CHCH₂ C—H C—HC—H 2.18 CH₃ H H C—CHCH₂ C—H C—H C—H 2.19 CH₃ OH H C—CHCH₂ C—H C—H C—H2.20 H H H C—H C—CHCH₂ C—H C—H 2.21 H OH H C—H C—CHCH₂ C—H C—H 2.22 CH₃H H C—H C—CHCH₂ C—H C—H 2.23 CH₃ OH H C—H C—CHCH₂ C—H C—H 2.24 H H H C—HC—H C—CHCH₂ C—H 2.25 H OH H C—H C—H C—CHCH₂ C—H 2.26 CH₃ H H C—H C—HC—CHCH₂ C—H 2.27 CH₃ OH H C—H C—H C—CHCH₂ C—H 2.28 H H H C—H C—H C—HC—CHCH₂ 2.29 H OH H C—H C—H C—H C—CHCH₂ 2.30 CH₃ H H C—H C—H C—H C—CHCH₂2.31 CH₃ OH H C—H C—H C—H C—CHCH₂ 2.32 H H H C—CH₂CHCH₂ C—H C—H C—H 2.33H OH H C—CH₂CHCH₂ C—H C—H C—H 2.34 CH₃ H H C—CH₂CHCH₂ C—H C—H C—H 2.35CH₃ OH H C—CH₂CHCH₂ C—H C—H C—H 2.36 H H H C—H C—CH₂CHCH₂ C—H C—H 2.37 HOH H C—H C—CH₂CHCH₂ C—H C—H 2.38 CH₃ H H C—H C—CH₂CHCH₂ C—H C—H 2.39 CH₃OH H C—H C—CH₂CHCH₂ C—H C—H 2.40 H H H C—H C—H C—CH₂CHCH₂ C—H 2.41 H OHH C—H C—H C—CH₂CHCH₂ C—H 2.42 CH₃ H H C—H C—H C—CH₂CHCH₂ C—H 2.43 CH₃ OHH C—H C—H C—CH₂CHCH₂ C—H 2.44 H H H C—H C—H C—H C—CH₂CHCH₂ 2.45 H OH HC—H C—H C—H C—CH₂CHCH₂ 2.46 CH₃ H H C—H C—H C—H C—CH₂CHCH₂ 2.47 CH₃ OH HC—H C—H C—H C—CH₂CHCH₂ 2.48 H H H C—CCCH₃ C—H C—H C—H 2.49 H OH HC—CCCH₃ C—H C—H C—H 2.50 CH₃ H H C—CCCH₃ C—H C—H C—H 2.51 CH₃ OH HC—CCCH₃ C—H C—H C—H 2.52 H H H C—H C—CCCH₃ C—H C—H 2.53 H OH H C—HC—CCCH₃ C—H C—H 2.54 CH₃ H H C—H C—CCCH₃ C—H C—H 2.55 CH₃ OH H C—HC—CCCH₃ C—H C—H 2.56 H H H C—H C—H C—CCCH₃ C—H 2.57 H OH H C—H C—HC—CCCH₃ C—H 2.58 CH₃ H H C—H C—H C—CCCH₃ C—H 2.59 CH₃ OH H C—H C—HC—CCCH₃ C—H 2.60 H H H C—H C—H C—H C—CCCH₃ 2.61 H OH H C—H C—H C—HC—CCCH₃ 2.62 CH₃ H H C—H C—H C—H C—CCCH₃ 2.63 CH₃ OH H C—H C—H C—HC—CCCH₃ 2.64 H H H C—Ph C—H C—H C—H 2.65 H OH H C—Ph C—H C—H C—H 2.66CH₃ H H C—Ph C—H C—H C—H 2.67 CH₃ OH H C—Ph C—H C—H C—H 2.68 H H H C—HC—Ph C—H C—H 2.69 H OH H C—H C—Ph C—H C—H 2.70 CH₃ H H C—H C—Ph C—H C—H2.71 CH₃ OH H C—H C—Ph C—H C—H 2.72 H H H C—H C—H C—Ph C—H 2.73 H OH HC—H C—H C—Ph C—H 2.74 CH₃ H H C—H C—H C—Ph C—H 2.75 CH₃ OH H C—H C—HC—Ph C—H 2.76 H H H C—H C—H C—H C—Ph 2.77 H OH H C—H C—H C—H C—Ph 2.78CH₃ H H C—H C—H C—H C—Ph 2.79 CH₃ OH H C—H C—H C—H C—Ph 2.80 H H HC—CH(CH₂)₂ C—H C—H C—H 2.81 H OH H C—CH(CH₂)₂ C—H C—H C—H 2.82 CH₃ H HC—CH(CH₂)₂ C—H C—H C—H 2.83 CH₃ OH H C—CH(CH₂)₂ C—H C—H C—H 2.84 H H HC—H C—CH(CH₂)₂ C—H C—H 2.85 H OH H C—H C—CH(CH₂)₂ C—H C—H 2.86 CH₃ H HC—H C—CH(CH₂)₂ C—H C—H 2.87 CH₃ OH H C—H C—CH(CH₂)₂ C—H C—H 2.88 H H HC—H C—H C—CH(CH₂)₂ C—H 2.89 H OH H C—H C—H C—CH(CH₂)₂ C—H 2.90 CH₃ H HC—H C—H C—CH(CH₂)₂ C—H 2.91 CH₃ OH H C—H C—H C—CH(CH₂)₂ C—H 2.92 H H HC—H C—H C—H C—CH(CH₂)₂ 2.93 H OH H C—H C—H C—H C—CH(CH₂)₂ 2.94 CH₃ H HC—H C—H C—H C—CH(CH₂)₂ 2.95 CH₃ OH H C—H C—H C—H C—CH(CH₂)₂ 2.96 H H H3-pyridyl C—H C—H C—H 2.97 H OH H 3-pyridyl C—H C—H C—H 2.98 CH₃ H H3-pyridyl C—H C—H C—H 2.99 CH₃ OH H 3-pyridyl C—H C—H C—H 2.100 H H HC—H 3-pyridyl C—H C—H 2.101 H OH H C—H 3-pyridyl C—H C—H 2.102 CH₃ H HC—H 3-pyridyl C—H C—H 2.103 CH₃ OH H C—H 3-pyridyl C—H C—H 2.104 H H HC—H C—H 3-pyridyl C—H 2.105 H OH H C—H C—H 3-pyridyl C—H 2.106 CH₃ H HC—H C—H 3-pyridyl C—H 2.107 CH₃ OH H C—H C—H 3-pyridyl C—H 2.108 H H HC—H C—H C—H 3-pyridyl 2.109 H OH H C—H C—H C—H 3-pyridyl 2.110 CH₃ H HC—H C—H C—H 3-pyridyl 2.111 CH₃ OH H C—H C—H C—H 3-pyridyl 2.112 H H H2-pyridyl C—H C—H C—H 2.113 H OH H 2-pyridyl C—H C—H C—H 2.114 CH₃ H H2-pyridyl C—H C—H C—H 2.115 CH₃ OH H 2-pyridyl C—H C—H C—H 2.116 H H HC—H 2-pyridyl C—H C—H 2.117 H OH H C—H 2-pyridyl C—H C—H 2.118 CH₃ H HC—H 2-pyridyl C—H C—H 2.119 CH₃ OH H C—H 2-pyridyl C—H C—H 2.120 H H HC—H C—H 2-pyridyl C—H 2.121 H OH H C—H C—H 2-pyridyl C—H 2.122 CH₃ H HC—H C—H 2-pyridyl C—H 2.123 CH₃ OH H C—H C—H 2-pyridyl C—H 2.124 H H HC—H C—H C—H 2-pyridyl 2.125 H OH H C—H C—H C—H 2-pyridyl 2.126 CH₃ H HC—H C—H C—H 2-pyridyl 2.127 CH₃ OH H C—H C—H C—H 2-pyridyl 2.128 H H HC—CO₂Me C—H C—H C—H 2.129 H OH H C—CO₂Me C—H C—H C—H 2.130 CH₃ H HC—CO₂Me C—H C—H C—H 2.131 CH₃ OH H C—CO₂Me C—H C—H C—H 2.132 H H H C—HC—CO₂Me C—H C—H 2.133 H OH H C—H C—CO₂Me C—H C—H 2.134 CH₃ H H C—HC—CO₂Me C—H C—H 2.135 CH₃ OH H C—H C—CO₂Me C—H C—H 2.136 H H H C—H C—HC—CO₂Me C—H 2.137 H OH H C—H C—H C—CO₂Me C—H 2.138 CH₃ H H C—H C—HC—CO₂Me C—H 2.139 CH₃ OH H C—H C—H C—CO₂Me C—H 2.140 H H H C—H C—H C—HC—CO₂Me 2.141 H OH H C—H C—H C—H C—CO₂Me 2.142 CH₃ H H C—H C—H C—HC—CO₂Me 2.143 CH₃ OH H C—H C—H C—H C—CO₂Me

The compounds of Formula (I) according to the invention can be used asplant growth regulators or seed germination promoters by themselves, butthey are generally formulated into plant growth regulation or seedgermination promotion compositions using formulation adjuvants, such ascarriers, solvents and surface-active agents (SFAs). Thus, the presentinvention further provides a plant growth regulator compositioncomprising a plant growth regulation compound of Formula (I) and anagriculturally acceptable formulation adjuvant. The present inventionfurther provides a plant growth regulator composition consistingessentially of a plant growth regulation compound of Formula (I) and anagriculturally acceptable formulation adjuvant. The present inventionfurther provides a plant growth regulator composition consisting of aplant growth regulation compound of Formula (I) and an agriculturallyacceptable formulation adjuvant. The present invention further providesa seed germination promoter composition comprising a seed germinationpromoter compound of Formula (I) and an agriculturally acceptableformulation adjuvant. The present invention further provides a seedgermination promoter composition consisting essentially of a seedgermination promoter compound of Formula (I) and an agriculturallyacceptable formulation adjuvant. The present invention further providesa seed germination promoter composition consisting of a seed germinationpromoter compound of Formula (I) and an agriculturally acceptableformulation adjuvant. The composition can be in the form of concentrateswhich are diluted prior to use, although ready-to-use compositions canalso be made. The final dilution is usually made with water, but can bemade instead of, or in addition to, water, with, for example, liquidfertilisers, micronutrients, biological organisms, oil or solvents.

The compositions generally comprise from 0.1 to 99% by weight,especially from 0.1 to 95% by weight, compounds of Formula (I) and from1 to 99.9% by weight of a formulation adjuvant which preferably includesfrom 0 to 25% by weight of a surface-active substance.

The compositions can be chosen from a number of formulation types, manyof which are known from the Manual on Development and Use of FAOSpecifications for Plant Protection Products, 5th Edition, 1999. Theseinclude dustable powders (DP), soluble powders (SP), water solublegranules (SG), water dispersible granules (WG), wettable powders (WP),granules (GR) (slow or fast release), soluble concentrates (SL), oilmiscible liquids (OL), ultra low volume liquids (UL), emulsifiableconcentrates (EC), dispersible concentrates (DC), emulsions (both oil inwater (EW) and water in oil (EO)), microemulsions (ME), suspensionconcentrates (SC), aerosols, capsule suspensions (CS) and seed treatmentformulations. The formulation type chosen in any instance will dependupon the particular purpose envisaged and the physical, chemical andbiological properties of the compound of Formula (I).

Dustable powders (DP) may be prepared by mixing a compound of Formula(I) with one or more solid diluents (for example natural clays, kaolin,pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk,diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulphur, lime, flours, talc and other organic and inorganicsolid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of Formula (I)with one or more water-soluble inorganic salts (such as sodiumbicarbonate, sodium carbonate or magnesium sulphate) or one or morewater-soluble organic solids (such as a polysaccharide) and, optionally,one or more wetting agents, one or more dispersing agents or a mixtureof said agents to improve water dispersibility/solubility. The mixtureis then ground to a fine powder. Similar compositions may also begranulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of Formula(I) with one or more solid diluents or carriers, one or more wettingagents and, preferably, one or more dispersing agents and, optionally,one or more suspending agents to facilitate the dispersion in liquids.The mixture is then ground to a fine powder. Similar compositions mayalso be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of acompound of Formula (I) and one or more powdered solid diluents orcarriers, or from pre-formed blank granules by absorbing a compound ofFormula (I) (or a solution thereof, in a suitable agent) in a porousgranular material (such as pumice, attapulgite clays, fuller's earth,kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing acompound of Formula (I) (or a solution thereof, in a suitable agent) onto a hard core material (such as sands, silicates, mineral carbonates,sulphates or phosphates) and drying if necessary. Agents which arecommonly used to aid absorption or adsorption include solvents (such asaliphatic and aromatic petroleum solvents, alcohols, ethers, ketones andesters) and sticking agents (such as polyvinyl acetates, polyvinylalcohols, dextrins, sugars and vegetable oils). One or more otheradditives may also be included in granules (for example an emulsifyingagent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compoundof Formula (I) in water or an organic solvent, such as a ketone, alcoholor glycol ether. These solutions may contain a surface active agent (forexample to improve water dilution or prevent crystallisation in a spraytank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may beprepared by dissolving a compound of Formula (I) in an organic solvent(optionally containing one or more wetting agents, one or moreemulsifying agents or a mixture of said agents). Suitable organicsolvents for use in ECs include aromatic hydrocarbons (such asalkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),ketones (such as cyclohexanone or methylcyclohexanone) and alcohols(such as benzyl alcohol, furfuryl alcohol or butanol),N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone),dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide)and chlorinated hydrocarbons. An EC product may spontaneously emulsifyon addition to water, to produce an emulsion with sufficient stabilityto allow spray application through appropriate equipment.

Preparation of an EW involves obtaining a compound of Formula (I) eitheras a liquid (if it is not a liquid at room temperature, it may be meltedat a reasonable temperature, typically below 70° C.) or in solution (bydissolving it in an appropriate solvent) and then emulsifying theresultant liquid or solution into water containing one or more SFAs,under high shear, to produce an emulsion. Suitable solvents for use inEWs include vegetable oils, chlorinated hydrocarbons (such aschlorobenzenes), aromatic solvents (such as alkylbenzenes oralkylnaphthalenes) and other appropriate organic solvents which have alow solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of oneor more solvents with one or more SFAs, to produce spontaneously athermodynamically stable isotropic liquid formulation. A compound ofFormula (I) is present initially in either the water or the solvent/SFAblend. Suitable solvents for use in MEs include those hereinbeforedescribed for use in ECs or in EWs. An ME may be either an oil-in-wateror a water-in-oil system (which system is present may be determined byconductivity measurements) and may be suitable for mixing water-solubleand oil-soluble pesticides in the same formulation. An ME is suitablefor dilution into water, either remaining as a microemulsion or forminga conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueoussuspensions of finely divided insoluble solid particles of a compound ofFormula (I). SCs may be prepared by ball or bead milling the solidcompound of Formula (I) in a suitable medium, optionally with one ormore dispersing agents, to produce a fine particle suspension of thecompound. One or more wetting agents may be included in the compositionand a suspending agent may be included to reduce the rate at which theparticles settle. Alternatively, a compound of Formula (I) may be drymilled and added to water, containing agents hereinbefore described, toproduce the desired end product.

Aerosol formulations comprise a compound of Formula (I) and a suitablepropellant (for example n-butane). A compound of Formula (I) may also bedissolved or dispersed in a suitable medium (for example water or awater miscible liquid, such as n-propanol) to provide compositions foruse in non-pressurised, hand-actuated spray pumps.

Capsule suspensions (CS) may be prepared in a manner similar to thepreparation of EW formulations but with an additional polymerisationstage such that an aqueous dispersion of oil droplets is obtained, inwhich each oil droplet is encapsulated by a polymeric shell and containsa compound of Formula (I) and, optionally, a carrier or diluenttherefor. The polymeric shell may be produced by either an interfacialpolycondensation reaction or by a coacervation procedure. Thecompositions may provide for controlled release of the compound ofFormula (I) and they may be used for seed treatment. A compound ofFormula (I) may also be formulated in a biodegradable polymeric matrixto provide a slow, controlled release of the compound.

The composition may include one or more additives to improve thebiological performance of the composition, for example by improvingwetting, retention or distribution on surfaces; resistance to rain ontreated surfaces; or uptake or mobility of a compound of Formula (I).Such additives include surface active agents (SFAs), spray additivesbased on oils, for example certain mineral oils or natural plant oils(such as soy bean and rape seed oil), and blends of these with otherbio-enhancing adjuvants (ingredients which may aid or modify the actionof a compound of Formula (I)).

Wetting agents, dispersing agents and emulsifying agents may be SFAs ofthe cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds(for example cetyltrimethyl ammonium bromide), imidazolines and aminesalts.

Suitable anionic SFAs include alkali metals salts of fatty acids, saltsof aliphatic monoesters of sulphuric acid (for example sodium laurylsulphate), salts of sulphonated aromatic compounds (for example sodiumdodecylbenzenesulphonate, calcium dodecylbenzenesulphonate,butylnaphthalene sulphonate and mixtures of sodium di-isopropyl- andtri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ethersulphates (for example sodium laureth-3-sulphate), ether carboxylates(for example sodium laureth-3-carboxylate), phosphate esters (productsfrom the reaction between one or more fatty alcohols and phosphoric acid(predominately mono-esters) or phosphorus pentoxide (predominatelydi-esters), for example the reaction between lauryl alcohol andtetraphosphoric acid; additionally these products may be ethoxylated),sulphosuccinamates, paraffin or olefine sulphonates, taurates andlignosulphonates.

Suitable SFAs of the amphoteric type include betaines, propionates andglycinates.

Suitable SFAs of the non-ionic type include condensation products ofalkylene oxides, such as ethylene oxide, propylene oxide, butylene oxideor mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetylalcohol) or with alkylphenols (such as octylphenol, nonylphenol oroctylcresol); partial esters derived from long chain fatty acids orhexitol anhydrides; condensation products of said partial esters withethylene oxide; block polymers (comprising ethylene oxide and propyleneoxide); alkanolamides; simple esters (for example fatty acidpolyethylene glycol esters); amine oxides (for example lauryl dimethylamine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such aspolysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose)and swelling clays (such as bentonite or attapulgite).

The present invention still further provides a method for regulating thegrowth of plants in a locus, wherein the method comprises application tothe locus of a plant growth regulating amount of a composition accordingto the present invention.

The present invention also provides a method for promoting thegermination of seeds, comprising applying to the seeds, or to a locuscontaining seeds, a seed germination promoting amount of a compositionaccording to the present invention.

The application is generally made by spraying the composition, typicallyby tractor mounted sprayer for large areas, but other methods such asdusting (for powders), drip or drench can also be used. Alternativelythe composition may be applied in furrow or directly to a seed before orat the time of planting.

The compound of Formula (I) or composition of the present invention maybe applied to a plant, part of the plant, plant organ, plant propagationmaterial or a surrounding area thereof.

In one embodiment, the invention relates to a method of treating a plantpropagation material comprising applying to the plant propagationmaterial a composition of the present invention in an amount effectiveto promote germination and/or regulate plant growth. The invention alsorelates to a plant propagation material treated with a compound ofFormula (I) or a composition of the present invention. Preferably, theplant propagation material is a seed. In an embodiment of the invention,the plant of the seed is selected from the genus brassica. The seed isin such an embodiment selected from the genus brassica. Common types ofbrassica include cabbage, cauliflower, broccoli, Brussel sprouts.

The term “plant propagation material” denotes all the generative partsof the plant, such as seeds, which can be used for the multiplication ofthe latter and vegetative plant materials such as cuttings and tubers.In particular, there may be mentioned the seeds, roots, fruits, tubers,bulbs, and rhizomes.

Methods for applying active ingredients to plant propagation material,especially seeds, are known in the art, and include dressing, coating,pelleting and soaking application methods of the propagation material.The treatment can be applied to the seed at any time between harvest ofthe seed and sowing of the seed or during the sowing process. The seedmay also be primed either before or after the treatment. The compound offormula (I) may optionally be applied in combination with a controlledrelease coating or technology so that the compound is released overtime.

The composition of the present invention may be applied pre-emergence orpost-emergence. Suitably, where the composition is being used toregulate the growth of crop plants, it may be applied pre orpost-emergence, but preferably post-emergence of the crop. Where thecomposition is used to promote the germination of seeds, it may beapplied pre-emergence.

The rates of application of compounds of Formula (I) may vary withinwide limits and depend on the nature of the soil, the method ofapplication (pre- or post-emergence; seed dressing; application to theseed furrow; no tillage application etc.), the crop plant, theprevailing climatic conditions, and other factors governed by the methodof application, the time of application and the target crop. For foliaror drench application, the compounds of Formula (I) according to theinvention are generally applied at a rate of from 1 to 2000 g/ha,especially from 5 to 1000 g/ha. For seed treatment the rate ofapplication is generally between 0.0005 and 150 g per 100 kg of seed.

Plants in which the composition according to the invention can be usedinclude crops such as cereals (for example wheat, barley, rye, oats);beet (for example sugar beet or fodder beet); fruits (for example pomes,stone fruits or soft fruits, such as apples, pears, plums, peaches,almonds, cherries, strawberries, raspberries or blackberries);leguminous plants (for example beans, lentils, peas or soybeans); oilplants (for example rape, mustard, poppy, olives, sunflowers, coconut,castor oil plants, cocoa beans or groundnuts); cucumber plants (forexample marrows, cucumbers or melons); fibre plants (for example cotton,flax, hemp or jute); citrus fruit (for example oranges, lemons,grapefruit or mandarins); vegetables (for example spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits orpaprika); lauraceae (for example avocados, cinnamon or camphor); maize;rice; tobacco; nuts; coffee; sugar cane; tea; vines; hops; durian;bananas; natural rubber plants; turf or ornamentals (for exampleflowers, shrubs, broad-leaved trees or evergreens such as conifers).This list does not represent any limitation.

The invention may also be used to regulate the growth, or promote thegermination of seeds of non-crop plants, for example to facilitate weedcontrol by synchronizing germination.

Crops are to be understood as also including those crops which have beenmodified by conventional methods of breeding or by genetic engineering.For example, the invention may be used in conjunction with crops thathave been rendered tolerant to herbicides or classes of herbicides (e.g.ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors). An example of acrop that has been rendered tolerant to imidazolinones, e.g. imazamox,by conventional methods of breeding is Clearfield® summer rape (canola).Examples of crops that have been rendered tolerant to herbicides bygenetic engineering methods include e.g. glyphosate- andglufosinate-resistant maize varieties commercially available under thetrade names RoundupReady® and LibertyLink®. Methods of rending cropplants tolerant to HPPD-inhibitors are known, for example fromWO0246387; for example the crop plant is transgenic in respect of apolynucleotide comprising a DNA sequence which encodes an HPPD-inhibitorresistant HPPD enzyme derived from a bacterium, more particularly fromPseudomonas fluorescens or Shewanella colwelliana, or from a plant, moreparticularly, derived from a monocot plant or, yet more particularly,from a barley, maize, wheat, rice, Brachiaria, Chenchrus, Lolium,Festuca, Setaria, Eleusine, Sorghum or Avena species.

Crops are also to be understood as being those which have been renderedresistant to harmful insects by genetic engineering methods, for exampleBt maize (resistant to European corn borer), Bt cotton (resistant tocotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).Examples of Bt maize are the Bt 176 maize hybrids of NK® (SyngentaSeeds). The Bt toxin is a protein that is formed naturally by Bacillusthuringiensis soil bacteria. Examples of toxins, or transgenic plantsable to synthesise such toxins, are described in EP-A-451 878, EP-A-374753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examplesof transgenic plants comprising one or more genes that code for aninsecticidal resistance and express one or more toxins are KnockOut®(maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton),NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seedmaterial thereof can be both resistant to herbicides and, at the sametime, resistant to insect feeding (“stacked” transgenic events). Forexample, seed can have the ability to express an insecticidal Cry3protein while at the same time being tolerant to glyphosate.

Crops are also to be understood to include those which are obtained byconventional methods of breeding or genetic engineering and containso-called output traits (e.g. improved storage stability, highernutritional value and improved flavour).

Compounds and compositions of the present invention may be applied incombination with other active ingredients or products for use inagriculture, including insecticides, fungicides, herbicides, plantgrowth regulators, crop enhancing compounds, nutrients and biologicals.Examples of suitable mixing partners may be found in the PesticideManual, 15^(th) edition (published by the British Crop ProtectionCouncil). Such mixtures may be applied to a plant, plant propagationmaterial or plant growing locus either simultaneously (for example as apre-formulated mixture or a tank mix), or sequentially in a suitabletimescale. Co-application of pesticides with the present invention hasthe added benefit of minimising farmer time spent applying products tocrops.

In a further aspect of the present invention, the compounds orcomposition of the present invention may be applied in combination withone or more other compounds having a crop enhancement effect. Suchcompounds include micronutrients, saccharides, amino acids, flavonoids,quinines, and plant activators/growth stimulators. For example, suchcompounds include natural or synthetic hormones, auxins,brassinosteroids, gibberellins, abscisic acid, cytokinins, jasmonates,strigolactones, salicylic acid, ethylene, 1-methylcyclopropene,trinexapac-ethyl or derivatives thereof. Such compounds also includepesticides that have a crop enhancement effect, for example strobilurins(including azoxystrobin, pyraclostrobin), and neonicotinoids (includingthiamethoxam, and imidacloprid).

It has now been found that these strigolactam derivatives according tothe invention also show crop enhancement effects.

Accordingly, the present invention provides a method of enhancing and/orincreasing the yield of crop plants by applying to the plants, plantparts, plant propagation material, or a plant growing locus, a compoundof formula (I).

The term “increasing the yield” of a plant means that the yield of aproduct of the plant is increased by a measurable amount over the yieldof the same product of the plant produced under the same conditions, butwithout the application of the combinations according to the presentinvention. It is preferred that the yield is increased by at least about0.5%, preferably 1%, more preferably 2%, yet more preferably 4% or more.Even more preferred is an increase in yield of at least about 5%, 10%,15% or 20% or more.

According to the present invention, ‘crop enhancement’ means animprovement in plant vigour, an improvement in plant quality, improvedtolerance to stress factors, and/or improved input use efficiency.

According to the present invention, an ‘improvement in plant vigour’means that certain traits are improved qualitatively or quantitativelywhen compared with the same trait in a control plant which has beengrown under the same conditions in the absence of the method of theinvention. Such traits include, but are not limited to, early and/orimproved germination, improved emergence, the ability to use less seeds,increased root growth, a more developed root system, increased rootnodulation, increased shoot growth, increased tillering, strongertillers, more productive tillers, increased or improved plant stand,less plant verse (lodging), an increase and/or improvement in plantheight, an increase in plant weight (fresh or dry), bigger leaf blades,greener leaf colour, increased pigment content, increased photosyntheticactivity, earlier flowering, longer panicles, early grain maturity,increased seed, fruit or pod size, increased pod or ear number,increased seed number per pod or ear, increased seed mass, enhanced seedfilling, less dead basal leaves, delay of senescence, improved vitalityof the plant, increased levels of amino acids in storage tissues and/orless inputs needed (e.g. less fertiliser, water and/or labour needed). Aplant with improved vigour may have an increase in any of theaforementioned traits or any combination or two or more of theaforementioned traits.

According to the present invention, an ‘improvement in plant quality’means that certain traits are improved qualitatively or quantitativelywhen compared with the same trait in a control plant which has beengrown under the same conditions in the absence of the method of theinvention. Such traits include, but are not limited to, improved visualappearance of the plant, reduced ethylene (reduced production and/orinhibition of reception), improved quality of harvested material, e.g.seeds, fruits, leaves, vegetables (such improved quality may manifest asimproved visual appearance of the harvested material), improvedcarbohydrate content (e.g. increased quantities of sugar and/or starch,improved sugar acid ratio, reduction of reducing sugars, increased rateof development of sugar), improved protein content, improved oil contentand composition, improved nutritional value, reduction inanti-nutritional compounds, improved organoleptic properties (e.g.improved taste) and/or improved consumer health benefits (e.g. increasedlevels of vitamins and anti-oxidants)), improved post-harvestcharacteristics (e.g. enhanced shelf-life and/or storage stability,easier processability, easier extraction of compounds), more homogenouscrop development (e.g. synchronised germination, flowering and/orfruiting of plants), and/or improved seed quality (e.g. for use infollowing seasons). A plant with improved quality may have an increasein any of the aforementioned traits or any combination or two or more ofthe aforementioned traits.

According to the present invention, an ‘improved tolerance to stressfactors’ means that certain traits are improved qualitatively orquantitatively when compared with the same trait in a control plantwhich has been grown under the same conditions in the absence of themethod of the invention. Such traits include, but are not limited to, anincreased tolerance and/or resistance to abiotic stress factors whichcause sub-optimal growing conditions such as drought (e.g. any stresswhich leads to a lack of water content in plants, a lack of water uptakepotential or a reduction in the water supply to plants), cold exposure,heat exposure, osmotic stress, UV stress, flooding, increased salinity(e.g. in the soil), increased mineral exposure, ozone exposure, highlight exposure and/or limited availability of nutrients (e.g. nitrogenand/or phosphorus nutrients). A plant with improved tolerance to stressfactors may have an increase in any of the aforementioned traits or anycombination or two or more of the aforementioned traits. In the case ofdrought and nutrient stress, such improved tolerances may be due to, forexample, more efficient uptake, use or retention of water and nutrients.

According to the present invention, an ‘improved input use efficiency’means that the plants are able to grow more effectively using givenlevels of inputs compared to the grown of control plants which are grownunder the same conditions in the absence of the method of the invention.In particular, the inputs include, but are not limited to fertiliser(such as nitrogen, phosphorous, potassium, micronutrients), light andwater. A plant with improved input use efficiency may have an improveduse of any of the aforementioned inputs or any combination of two ormore of the aforementioned inputs.

Other crop enhancements of the present invention include a decrease inplant height, or reduction in tillering, which are beneficial featuresin crops or conditions where it is desirable to have less biomass andfewer tillers.

Crop enhancement also includes safening of crop plants againstphytotoxic effects of pesticides or other compounds that are applied tothe crop.

Any or all of the above crop enhancements may lead to an improved yieldby improving e.g. plant physiology, plant growth and development and/orplant architecture. In the context of the present invention ‘yield’includes, but is not limited to, (i) an increase in biomass production,grain yield, starch content, oil content and/or protein content, whichmay result from (a) an increase in the amount produced by the plant perse or (b) an improved ability to harvest plant matter, (ii) animprovement in the composition of the harvested material (e.g. improvedsugar acid ratios, improved oil composition, increased nutritionalvalue, reduction of anti-nutritional compounds, increased consumerhealth benefits) and/or (iii) an increased/facilitated ability toharvest the crop, improved processability of the crop and/or betterstorage stability/shelf life. Increased yield of an agricultural plantmeans that, where it is possible to take a quantitative measurement, theyield of a product of the respective plant is increased by a measurableamount over the yield of the same product of the plant produced underthe same conditions, but without application of the present invention.According to the present invention, it is preferred that the yield beincreased by at least 0.5%, more preferred at least 1%, even morepreferred at least 2%, still more preferred at least 4%, preferably 5%or even more.

Any or all of the above crop enhancements may also lead to an improvedutilisation of land, i.e. land which was previously unavailable orsub-optimal for cultivation may become available. For example, plantswhich show an increased ability to survive in drought conditions, may beable to be cultivated in areas of sub-optimal rainfall, e.g. perhaps onthe fringe of a desert or even the desert itself.

In one aspect of the present invention, crop enhancements are made inthe substantial absence of pressure from pests and/or diseases and/orabiotic stress. In a further aspect of the present invention,improvements in plant vigour, stress tolerance, quality and/or yield aremade in the substantial absence of pressure from pests and/or diseases.For example pests and/or diseases may be controlled by a pesticidaltreatment that is applied prior to, or at the same time as, the methodof the present invention. In a still further aspect of the presentinvention, improvements in plant vigour, stress tolerance, qualityand/or yield are made in the absence of pest and/or disease pressure. Ina further embodiment, improvements in plant vigour, quality and/or yieldare made in the absence, or substantial absence, of abiotic stress.

According to the present invention, there is provided the use of acompound of formula (I) or a composition comprising a compound offormula (I) for improving plant yield, plant vigour, plant quality,plant tolerance to stress factors and/or plant input use efficiency.

Crop enhancement may be achieved in a range of crops. Suitable targetcrops are, in particular, cereals, such as wheat, barley, rye, oats,rice, maize or sorghum. However, preferably the crop plants are selectedfrom the group consisting of corn, wheat, rice, soybean.

The compounds of the invention may be made by the following methods.

Compounds of Formula (VI) within R is C₁-C₆ alkyl and W is oxygen may beprepared from compounds of Formula (VII) by esterification by treatmentwith an alcohol in presence of an acid, such sulphuric acid in methanolor ethanol. Alternatively, compounds of Formula (VI) may be preparedfrom commercial or not starting material such as indanone derivatives asdescribed in literature (see for example: Bioorganic & MedicinalChemistry (2008), 16(8), p. 4438; Journal of the Chemical Society,Perkin Transactions 1: Organic and Bio-Organic Chemistry (1999), (18),p. 2617; WO2005097093; Monatshefte fuer Chemie (1986), 117(5), p. 621).Indanone derivatives can be prepared by known method to the personskilled in the art.

i) Compounds of Formula (III) may be prepared from a compound of Formula(VI) wherein R is not a hydrogen such as for example R is a methyl orethyl via reductive amination by reaction of an substituted amine suchas methyl amine and a reducing agent such as sodium cyanoborohydridefollowed by in situ intramolecular cyclisation.ii) Alternatively, compounds of Formula (IIIa) may be prepared from acompound of Formula (VI) wherein R is H via reductive amination byreaction of an amine such as ammonium acetate and a reducing agent suchas sodium cyanoborohydride followed by in situ intramolecularcyclisation.iii) Alternatively, compounds of Formula (IIIa) can be prepared from acompound of Formula (VI) via formation of the oxime using ahydroxylamine salt and a base such as sodium acetate or pyridine,followed by reduction of the intermediate oxime using hydrogenation withH₂ and a catalyst such as Pd/C or Raney Nickel, or other known methodssuch as zinc in acetic acid.Compounds of formula (III), wherein R1 is an aromatic or heteroaromaticgroup, may be prepared from a compound of formula (IIIa) (wherein R1 isH) by reaction of the amide with an aromatic or heteroaromatic compoundof formula ArX, X being an halogen, in the presence of a base such aspotassium phosphate and a suitable catalyst, often a copper (I) salt anda ligand such as dimethylethane-1,2-diamine.Compounds of Formula (III), wherein R1 is not hydrogen, may be preparedfrom a compound of formula (IIIa) (wherein R1 is H) via alkylation byreaction of the amide with an alkylating agent such as an alkyl halide,in the presence of a base such as sodium hydride.Compounds of Formula (III), wherein R1 is a carbonyl derivative, may beprepared by acylation of a compound of Formula (Ma) with a compound offormula (V), wherein R is OH, in the presence of a coupling reagent,such as DCC (N,N′-dicyclohexylcarbodiimide), EDC(1-ethyl-3-[3-dimethylamino-propyl]carbodiimide hydrochloride) or BOP-Cl(bis(2-oxo-3-oxazolidinyl)phosphonic chloride), in the presence of abase, such as pyridine, triethylamine, 4-(dimethylamino)pyridine ordiisopropylethylamine, and optionally in the presence of a nucleophiliccatalyst, such as hydroxybenzotriazole. Optionally, when R is Cl orOC(O)C₁-C₆alkoxy, the acylation reaction may be carried out under basicconditions (for example in the presence of pyridine, triethylamine,4-(dimethylamino)pyridine or diisopropylethylamine), optionally in thepresence of a nucleophilic catalyst. Alternatively, the reaction may beconducted in a biphasic system comprising an organic solvent, preferablyethyl acetate, and an aqueous solvent, preferably a solution of sodiumbicarbonate. Optionally, when R is C₁-C₆alkoxy, the amide may beprepared by heating the derivative (V) and amide (IIIa) together. R′ maybe alkyl or alkoxy group. In addition, Compounds of Formula (III) may beprepared, under racemic form as described in Journal of PharmaceuticalSciences (1973), 62(8), p. 1363; Journal of Organic Chemistry (1994),59(2), p. 284; Russian Journal of Organic Chemistry, (2005) 41(3), p.361; or WO84/00962.Compounds of Formula (III) or (IIIa) wherein A₁, A₂, A₃ and A₄ are asdescribed for the compound of Formula (I) can be prepared by thereaction of compounds of Formula (III) or (IIIa) wherein A₁, A₂, A₃ orA₄ are independently C-LG, wherein LG is a suitable leaving group, suchas, for example halogen or triflate with a derivative of formula Z—X,wherein Z is a boron or a tin derivatives and X is as described for thecompound of Formula (I) in the presence of a suitable catalyst/ligandsystem, often a palladium (0) complex. These reactions can be carriedout or not under microwave irradiation. These reactions being known tothe person skilled in the art under the name of Stille, Suzuki coupling,see for example: Strategic Applications of Named Reactions in OrganicSynthesis Kurti, Laszlo; Czako, Barbara; Editors. USA. (2005),Publisher: Elsevier Academic Press, Burlington, Mass. p. 448 (Suzukicoupling) and p. 438 (Stille coupling) and cited references.

Compounds of Formula (III) or (Ma) wherein A₁, A₂, A₃ and A₄ are is CCRwhere R is an C₁-C₆ alkyl, aryl, heteroaryl can also be prepared by thereaction of compounds of Formula (III) or (Ma) wherein A₁, A₂, A₃ or A₄are independently C-LG, wherein LG is a suitable leaving group, such asfor example halogen or triflate with a derivative of formula HCCR in thepresence of a suitable catalyst/ligand system, often a palladium (0)complex with or without a source of copper such as copper iodide and anorganic base such as diisopropylethyl amine. This reaction being knownto the person skilled in the art under the name of Sonogashira coupling,see for example: Strategic Applications of Named Reactions in OrganicSynthesis Kurti, Laszlo; Czako, Barbara; Editors. USA. (2005),Publisher: Elsevier Academic Press, Burlington, Mass. p. 424(Sonogashira coupling) and cited references.

Compounds of Formula (II) may be prepared from a compound of Formula(III) via reaction with a formic ester derivative such as the methylformate in presence of a base such as lithium diisopropylamide orpotassium tert-butylate. Alternatively, compounds of Formula (II) may beprepared from a compound of Formula (IV) via hydrolysis with an acidsuch as hydrogen chloride. Compounds of Formula (IV) may be preparedfrom a compounds of Formula (III) via reaction with a Bredereck'sreagent (t-Butoxybis(dimethylamino)methane) wherein R is methyl oranalogue.

Compounds of Formula (IIb) can be prepared from a compound of Formula(IIa) wherein R is an alkyl group such as tert butyl via treatment withan acid such as trifluoroacetic acid or hydrogen chloride.Alternatively, compounds of Formula (IIb) can be prepared from acompound of Formula (IVa) wherein R is an alkyl group such as tert butylvia treatment with an acid such as hydrogen chloride.

Compounds of Formula (I) may be prepared from a compounds of Formula(II) via nucleophilic substitution of a 5H-furanone derivative having aleaving group (LG) and LG is a leaving group, such as bromine inposition 5 in presence of a base such as for example potassiumtert-butylate.

Alternatively, compounds of Formula (I), wherein R1 is an alkylderivative or a benzyl derivative, may be prepared from a compound ofFormula (Ia) wherein R1 is H via alkylation by reaction of the aminewith an alkylating agent such as an alkyl halide, benzyl halideoptionally in the presence of a base such as sodium hydride.Alternatively, compounds of Formula (I), wherein a carbonyl derivative,may be prepared from a compound of Formula (Ia) wherein R1 is H viaacylation with a compound of Formula (V), wherein R is OH, in thepresence of a coupling reagent, such as DCC(N,N′-dicyclohexylcarbodiimide), EDC(1-ethyl-3-[3-dimethylamino-propyl]carbodiimide hydrochloride) or BOP-Cl(bis(2-oxo-3-oxazolidinyl)phosphonic chloride), in the presence of abase, such as pyridine, triethylamine, 4-(dimethylamino)pyridine ordiisopropylethylamine, and optionally in the presence of a nucleophiliccatalyst, such as hydroxybenzotriazole. Optionally, when R is Cl orOC(O)C₁-C₆alkoxy, the acylation reaction may be carried out under basicconditions (for example in the presence of pyridine, triethylamine,4-(dimethylamino)pyridine or diisopropylethylamine), optionally in thepresence of a nucleophilic catalyst. Alternatively, the reaction may beconducted in a biphasic system comprising an organic solvent, preferablyethyl acetate, and an aqueous solvent, preferably a solution of sodiumbicarbonate. Optionally, when R is C₁-C₆alkoxy, the amide may beprepared by heating the ester (V) and amide (Ia) together. R′ may bealkyl or alkoxy group. Compounds of Formula (I), wherein W is sulfur,may be prepared from a compound of Formula (I), wherein W is oxygen, bytreatment with a thio-transfer reagent, such as Lawesson's reagent orphosphorus pentasulfide.

EXAMPLES

The following HPLC-MS methods were used for the analysis of thecompounds:

Method A: Spectra were recorded on a ZQ (Waters Corp. Milford, Mass.,USA) mass spectrometer equipped with an electrospray source (ESI; sourcetemperature 100° C.; desolvation temperature 250° C.; cone voltage 30 V;cone gas flow 50 L/Hr, desolvation gas flow 400 L/Hr, mass range: 100 to900 Da) and an Agilent 1100 LC (column: Gemini C18, 3 um particle size,110 Angstrom, 30×3 mm (Phenomenex, Torrance, Calif., USA); columntemperature: 60° C.; flow rate 1.7 mL/min; eluent A: H₂O/HCO₂H 100:0.05;eluent B: MeCN/MeOH/HCO₂H 80:20:0.04; gradient: 0 min 5% B; 2-2.8 min100% B; 2.9-3 min 5% B; UV-detection: 200-500 nm, resolution 2 nm. Theflow was split postcolumn prior to MS analysis.Method B: Spectra were recorded on a SQD Mass Spectrometer (Waters Corp.Milford, Mass., USA) mass spectrometer equipped with an electrospraysource (ESI; source temperature 150° C.; desolvation temperature 250°C.; cone voltage 45 V; desolvation gas flow 650 L/Hr, mass range: 100 to900 Da) and an Agilent UP LC (column: Gemini C18, 3 um, 30×2 mm(Phenomenex, Torrance, Calif., USA); LC (column: Gemini C18, 3 umparticle size, 110 Angstrom, 30×3 mm (Phenomenex, Torrance, Calif.,USA); column temperature: 60° C.; flow rate 0.85 mL/min; eluent A:H₂O/MeOH/HCO₂H 100:5:0.05; eluent B: MeCN/HCOOH 100:0.05; gradient: 0min 0% B; 0-1.2 min 100% B; 1.2-1.50 min 100% B; UV-detection: 210-500nm, resolution 2 nm. The flow was split postcolumn prior to MS analysis.Method C: Spectra were recorded on a SQD Mass Spectrometer from Waters(Single quadrupole mass spectrometer) mass spectrometer equipped with anelectrospray source (Polarity: positive and negative ions, Capillary:3.00 kV, Cone: 30.00 V, Extractor: 2.00 V, Source Temperature: 150° C.,Desolvation Temperature: 250° C., Cone Gas Flow: 0 L/Hr, Desolvation GasFlow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC fromWaters (Binary pump, heated column compartment and diode-array detector,Solvent degasser, binary pump, heated column compartment and diode-arraydetector, Column: Phenomenex Gemini C18, 3 μm, 30×2 mm, Temp: 60° C.,flow rate 0.85 mL/min; DAD Wavelength range (nm): 210 to 500) SolventGradient: A=H₂O+5% MeOH+0.05% HCOOH, B=Acetonitril+0.05% HCOOH)gradient: 0 min 0% B; 0-1.2 min 100% B; 1.2-1.50 min 100% B.

The following abbreviations are used throughout this section: s=singlet;bs=broad singlet; d=doublet; dd=double doublet; dt=double triplet;t=triplet, tt=triple triplet, q=quartet, m=multiplet; Me=methyl;Et=ethyl; Pr=propyl; Bu=butyl; M.p.=melting point; RT=retention time,MH⁺=molecular cation (i.e. measured molecular weight).

Example 1 Synthesis of the diastereoisomer of(3aR,8bS,5′R)-5-allyl-3-[1-(4-Methyl-5-oxo-2,5-dihydro-furan-2-yloxy)-meth-(E)-ylidene]-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one(A1) and the diastereoisomer of(3aR*,8bS*,5'S*)-5-allyl-3-[1-(4-Methyl-5-oxo-2,5-dihydro-furan-2-yloxy)-meth-(E)-ylidene]-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one(B1) Step 1: (1-Oxo-4-bromo-indan-2-yl)-acetic acid ethyl ester

To a solution of 4-bromoindanone (15.8 g, 75 mmol) at −78° C. was addedLiHMDS (1 M in THF, 90 mL). The slight brown solution was allowed towarm up to 0° C., and was cooled again to −75° C. and ethyl2-bromoacetate (9.1 mL, 82 mmol) was added dropwise. The mixture wasallowed to warm up over night (−75° C. to −20° C. over 12 h). Themixture was quenched with sat. ammonium chloride and was extracted withethyl acetate. Flash chromatography give 19.5 g of the title compound ina mixture with the starting indanone ethyl2-[4-bromo-2-(2-ethoxy-2-oxo-ethyl)-1-oxo-indan-2-yl]acetate and whichwas used without further purification for the next step (purity, 60% ofthe desired product). LC-MS (Method A) RT 1.11 min., 297/299 (M+H⁺).

This method was used to prepare the (7-Bromo-1-oxo-indan-2-yl)-aceticacid ethyl ester. LC-MS (Method B) RT 0.90 min., 297/299 (M+H⁺).

Step 2: 5-Bromo-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one

To a solution of (1-Oxo-4-bromo-indan-2-yl)-acetic acid ethyl ester(3.47 g, 11.7 mmol) in methanol (90 mL) was added pyridine (1.88 mL,23.4 mmol) and hydroxylamine hydrochloride (1.22 g, 17.5 mmol). Thesolution was stirred overnight at room temperature, diluted with water,extracted with ethyl acetate, washed twice with a saturated solution ofsodium hydrogenocarbonte, dried over magnesium sulphate, filtered andconcentrated to give the corresponding oxime (2.90 g, 80%). The compoundwas used without extra purification for the next step.The oxime obtained in the preview step (4.30 g, 14.4 mmol) was taken upin acetic acid (50 mL) and heated to 60° C. Then, zinc dust (9.43 g,144.2 mmol) was added portionwise, keeping the temperature under 80° C.The solution was stirred for 30 min at 60° C. and was then filtered.Water was added to the filtrate and the solution was neutralized withsolid potassium carbonate until pH reaches 7. The solution was extractedwith dichloromethane, washed with aqueous HCl (1 N), dried andconcentrated to give the lactame (2.9 g, 80%) as a white solid. LC-MS(Method A) RT 1.43 min, 252/254 (M+H⁺).

This method was used to prepare the8-bromo-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one. LC-MS (MethodB) RT 0.69, 252/254 (M+H⁺).

Step 3: Tert-butyl5-bromo-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylate

To a suspension of5-bromo-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one (0.85 g, 3.4mmol) in anhydrous acetonitrile (50 mL) was added dimethylaminopyridine(0.04 g, 0.3 mmol), triethylamine (0.944 mL, 6.7 mmol) and di-t-butyldicarbonate (1.47 g, 6.7 mmol). The solution was stirred at roomtemperature overnight. The solution was diluted with ethyl acetate andwashed with hydrogen chloride (1 M) and brine. The combined organiclayers were dried and concentrated. The residue was purified by flashchromatography eluting with ethyl acetate and cyclohexane (2/8) to givethe desired product (480 mg). LC-MS (Method B) RT 1.02 min, 725/727/729(2M+Na⁺).

This method was used to prepare the Tert-butyl8-bromo-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylate.LC-MS (Method B) RT 0.97 min, 725/727/729 (2M+Na⁺).

Step 4: Tert-butyl5-allyl-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylate(E1)

A solution tert-butyl5-bromo-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylate(Step 3, 500 mg), Pd(PPh₃)₄ (80 mg, 0.1 equiv.), allyltributylstannate(0.56 g, 1.20 equiv.) in toluene (17 mL) was degassed and stirred atreflux overnight. The solvent was removed under vacuum. The residue wastaken up in acetonitrile (40 mL) and washed twice with n-hexane. Theacetonitrile was removed in vacuo and the residue was purified by flashchromatography eluting with ethyl acetate and cyclohexane (1 to 25%) togive 210 mg of the desired product E1; LCMS (Method B), RT: 1.05 min;ES+ 649 (2M+Na⁺).

Analogous procedures were used to prepare the following compounds E4 toE7 (table F) starting from the corresponding tributylstannane (allcommercially available).

Step 5: tert-butyl(3Z)-5-allyl-3-(dimethylaminomethylene)-2-oxo-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylate(D1)

A solution of the tert-butyl5-allyl-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylate(Step 4, 0.21 g, 0.7 mmol) in tert-butoxybis(dimethylamino)methane(0.415 mL, 2.0 mmol) in toluene (3 ml) was heated at 110° C. overnight.The solution was diluted with ethyl acetate and washed twice with water,brine, dried over magnesium sulphate and concentrated to give tert-butyl(3Z)-5-allyl-3-(dimethylaminomethylene)-2-oxo-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylateD1 (colourless solid, 0.24 g, 97%). This compound was used without extrapurification. LC-MS (Method C) RT 1.05 min, 369 (M+H⁺). This method wasused to prepare compound D2 to D13 (table D).

Step 6:(3Z)-5-allyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-oneC1

To a solution of tert-butyl(3Z)-5-allyl-3-(dimethylaminomethylene)-2-oxo-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylateD1 (Step 5, 0.24 g, 0.65 mmol) in dioxane (10 mL) was added HCl (37%,0.68 mL). The solution was stirred overnight at room temperature and wasthen diluted with water, extracted with ethyl acetate, washed withbrine, dried and concentrated to give 0.200 g of a mixture of(3Z)-5-allyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one and tert-butyl(3Z)-5-allyl-3-(hydroxymethylene)-2-oxo-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylate.A solution of 0.100 g of a mixture of(3Z)-5-allyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one and tert-butyl(3Z)-5-allyl-3-(hydroxymethylene)-2-oxo-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylatein dichloromethane (18 mL) was added trifluoroacetic acid (2 mL) at 0°C. The solution was stirred for 2.5 h at 0° C. A saturated solution ofsodium hydrogenocarbonate was added and the aqueous layer was extractedwith dichloromethane. The combined organic layers were washed with asaturated solution of sodium hydrogenocarbonate, dried and concentratedin vacuo to give (3Z)-5-allyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one C1 (70 mg, quant.). LC-MS (Method C) RT 0.75min; ES− 240 (M−H⁺).

Step 7: Example A1 and B1 Synthesis of the diastereoisomer(3aR*,8bS*,5′R*)-5-allyl-3-[1-(4-Methyl-5-oxo-2,5-dihydro-furan-2-yloxy)-meth-(E)-ylidene]-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one(A1) and the diastereoisomer(3aR*,8bS*,5'S*)-5-allyl-3-[1-(4-Methyl-5-oxo-2,5-dihydro-furan-2-yloxy)-meth-(E)-ylidene]-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one(B1)

To a solution of (3Z)-5-allyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one (Step 6, 0.070 g, 0.3 mmol) indimethylformamide (5 mL) cooled at 0° C. was added potassium tertbutoxide (0.036 g, 0.3 mmol). The solution was stirred for 10 min. and asolution of bromo butenolide (0.062 g, 0.3 mmol, prepared according toJohnson & all, J. C. S. Perkin I, 1981, 1734-1743) in tetrahydrofuran (1mL) was added. The solution was stirred at 0° C. for 3 h. The solutionwas partitioned between ethyl acetate and water and the aqueous layerwas extracted with ethyl acetate. The combined organic layer was washedwith brine, dried over magnesium sulfate and concentrated under vacuum.The residue was purified by flash chromatography eluting with a gradientof cyclohexane and ethyl acetate (50 to 80%) followed by an isocraticperiod of 80% of ethyl acetate and cyclohexane. Two diastereoisomerswere obtained:

diastereoisomer of(3aR*,8bS*,5′R*)-5-allyl-3-[1-(4-Methyl-5-oxo-2,5-dihydro-furan-2-yloxy)-meth-(E)-ylidene]-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one(A1) (less polar, 5.6 mg); LCMS (method C) RT 0.88 min; 338 (M+H⁺).

diastereoisomer of(3aR*,8bS*,5'S*)-5-allyl-3-[1-(4-Methyl-5-oxo-2,5-dihydro-furan-2-yloxy)-meth-(E)-ylidene]-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one(B1) (more polar, 5.30 mg); LCMS (method C) RT 0.86 min; 338 (M+H⁺).

A similar method was used to prepare compounds A2-A13 and B2-B13.

Example 2 Synthesis of the diastereoisomer(3aR*,8bS*,5′R*)-5-ethynyl-3-[1-(4-Methyl-5-oxo-2,5-dihydro-furan-2-yloxy)-meth-(E)-ylidene]-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one(A2) and the diastereoisomer(3aR*,8bS*,5'S*)-5-ethynyl-3-[1-(4-Methyl-5-oxo-2,5-dihydro-furan-2-yloxy)-meth-(E)-ylidene]-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one(B2) Step 1: Tert-butyl5-triethylethynyl-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylateE2

To a degassed solution of tert-butyl5-bromo-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylate(Example 1, Step 3, 500 mg) was successively added Pd(PPh₃)₂Cl₂ (0.1 g),copper iodine (0.04 g), trimethylsilyl acetylene (0.28 g, 0.4 mL) anddiisopropyl amine (0.40 mL). The reaction was stirred at 80° C. for 20h. The reaction was diluted with water and ethyl acetate and the aqueousphase was extracted twice with ethyl acetate and combined organic phasewere washed with HCl 1N and brine, dried over magnesium sulfate andconcentrated under vacuum. Flash chromatography with a gradient of ethylacetate in cyclohexane gave 130 mg (25%) of the desired product and 310mg of pure starting material (63%): LCMS (method C), RT: 1.22 min, [761,2M+Na+]. ¹H NMR (400 MHz, CDCl₃) δ 7.52 (1H, d), 7.39 (1H, d), 7.19 (1H,t), 5.61 (1H, d), 3.10-3.23 (2H, m), 2.93 (1H, m), 2.78 (1H, dd), 2.30(1H, dd), 1.61 (9H, s), 0.25 (9H, s) ppm.

Step 2: tert-butyl(3Z)-3-(dimethylaminomethylene)-2-oxo-5-(2-trimethylsilylethynyl)-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylateD2

The product was prepare in a similar manner to product D1 (Example 1,step 5) starting from tert-butyl5-trimethylethynyl-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylateE2 (Example 2, Step 1, 0.13 g, 0.4 mmol) give tert-butyl(3Z)-3-(dimethylaminomethylene)-2-oxo-5-(2-trimethylsilylethynyl)-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylateD2 (0.14 g, 94%). This compound was used without extra purification.LC-MS (Method C) RT 1.21, 425 (M+H⁺).

Step 3:((3Z)-5-ethynyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one(C2)

To a solution of tert-butyl(3Z)-3-(dimethylaminomethylene)-2-oxo-5-(2-trimethylsilylethynyl)-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylateD2 (Example 2, Step 2, 0.13 g, 0.3 mmol) in dioxane (5 mL) was added HCl(37%, 0.321 mL). The solution was stirred 2 h at room temperature andwas then diluted with water, extracted with ethyl acetate, washed withbrine, dried and concentrated to give 0.130 g of a mixture of tert-butyl(3Z)-3-(hydroxymethylene)-2-oxo-5-(2-trimethylsilylethynyl)-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylateand(3Z)-3-(hydroxymethylene)-5-(2-trimethylsilylethynyl)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one.A solution of 0.13 g of a mixture of tert-butyl(3Z)-3-(hydroxymethylene)-2-oxo-5-(2-trimethylsilylethynyl)-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylateand(3Z)-3-(hydroxymethylene)-5-(2-trimethylsilylethynyl)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-onein dichloromethane (18 mL) was added trifluoroacetic acid (2 mL) at 0°C. The solution was stirred for 1 h at 0° C. A saturated solution ofsodium hydrogenocarbonate was added and the aqueous layer was extractedwith dichloromethane. The combined organic layers were washed with asaturated solution of sodium hydrogenocarbonate, dried and concentratedin vacuo to give((3Z)-5-ethynyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-oneC2 (70 mg, 72%). LC-MS (Method C) RT 0.67 min, ES− 224 (M−H⁺), ES+226(M+H⁺).

Step 4: Diastereoisomer(3E,3aR,8bS)-5-ethynyl-3-[(4-methyl-5-oxo-2H-furan-2-yl)oxymethylene]-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one(A2) and diastereoisomer(3E,3aR,8bS)-5-ethynyl-3-[[(2S)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one(B2)

The product was prepare in a similar manner to product A1 and B1(Example 1, step 7) starting from((3Z)-5-ethynyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-oneC2 (Example 2, Step 3, 0.070 g, 0.3 mmol). Two diastereoisomers wereobtained: (A2) (less polar, 15 mg) and (B2) (more polar, 6 mg, imp).

diastereoisomer of(3E,3aR,8bS)-5-ethynyl-3-[(4-methyl-5-oxo-2H-furan-2-yl)oxymethylene]-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one(A2) (less polar, 14.9 mg); LCMS (method C) RT 0.80 min; 322 (M+H⁺).

diastereoisomer of(3E,3aR,8bS)-5-ethynyl-3-[[(2S)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one(B2) (more polar, 6.0 mg); LCMS (method C) RT 0.78 min; 322 (M+H⁺).

Example 3 Synthesis of the diastereoisomer of methyl(3E,3aR,8bR)-3-[[(2R)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-2-oxo-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-7-carboxylate(A3) and diastereoisomer methyl(3E,3aR,8bR)-3-[[(2S)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-2-oxo-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-7-carboxylate(B3)

This example was synthesized by a known method described in Journal ofAgricultural and Food Chemistry (1997), 45(6), p. 2278-2283 and Journalof Agricultural and Food Chemistry (1992), 40(7), p. 1230-5.

Step 1: 3-Oxo-indan-2,5-dicarboxylic acid 2-ethyl ester-5-methyl ester

To a stirred suspension of 3-oxo-indan-5-carboxylic acid methyl ester(commercially available, 300 mg, 1.5 mmol) in dry THF (7.3 ml) wascooled to −70° C. and a 1.0 M solution of lithiumbis(trimethylsilyl)amide in THF (3.4 ml, 3.4 mmol) was added drop wiseduring 20 mins. The reaction mixture was allowed to warm to −33° C.during 1 h and giving a reddish brown solution. The reaction mixture wasrecooled to −65° C. and ethyl cyano formate (239 mg, 0.24 ml, 2.4 mmol)was added during one min. The reaction mixture was allowed to warm up to15° C. during 3 h. The reaction mixture was partitioned between ethylacetate and 1 N HCl. Organic phases were successively washed with water,saturated NaHCO₃, brine and dried (Na₂SO₄). Solvent was evaporated todryness; solid obtained was washed with hexane, dried to yield a desiredcompound (295 mg. 71%).

¹H NMR (400 MHz, CDCl₃) δ 10.30 (0.25H, br, OH), 8.41 (0.75H, s), 8.30(1.5H, m), 8.11 (0.25H, m), 7.55 (1H, m), 4.30 (2H, m), 3.77 (3H, s),3.75 (0.75H, m), 3.63 (1.25H, m), 3.40 (0.75, m), 1.28 (3H, m) ppm(mixture of ketone and enol).

Step 2: 2-Ethoxycarbonylmethyl-3-oxo-indan-2,5-dicarboxylic acid-2-ethylester-5-methyl ester

To a stirred solution of 3-oxo-indan-2,5-dicarboxylic acid 2-ethylester-5-methyl ester (Step 1, 500 mg, 1.9 mmol) in dry DMF (0.7 ml) wasadded sodium hydride (84 mg, 2.0 mmol, 60% in mineral oil) and thenheated at 60° C. for 1 h. Then ethyl bromo acetate (350 mg, 2.0 mmol)was dissolved in dry DMF (1.4 ml) and added to the reaction mixture atroom temperature and then again heated at 60° C. for 3 h. Aftercompletion of the reaction mixture was concentrated and H₂O (5 ml) wasadded. The suspension was extracted with ethyl acetate and combinedorganic layer was washed with brine, dried and concentrated. The crudewas purified by column chromatography using 20% ethyl acetate-hexane togive the desired compound (530 mg). ¹H NMR (400 MHz, CDCl₃) d 8.42 (1H,s), 8.30 (1H, d), 7.57 (1H, d), 4.37 (4H, m), 3.92 (3H, s), 3.90 (1H,d), 3.28 (2H, m), 2.90 (1H, d), 1.15 (3H, m) ppm.

Step 3: methyl 2-(2-methoxy-2-oxo-ethyl)-3-oxo-indane-5-carboxylate

2-Ethoxycarbonylmethyl-3-oxo-indan-2,5-dicarboxylic acid-2-ethylester-5-methyl ester (Step 2, 530 mg, 1.5 mmol) in 1.3 ml mixture of 6 NHCl: acetic acid (1:1) was heated to reflux for 3 h. The reactionmixture was evaporated to dryness, 10 ml water was added and extractedwith ethyl acetate. Organic layer was washed with brine, dried oversodium sulphate and then concentrated. The crude product was washed withhexane and precede next step without further purification (530 mg).To a stirred solution of 2-carboxymethyl-3-oxo-indan-5-carboxylic acid(3.5 g, 14.9 mmol) in methanol (53 ml) was added concentrated sulphuricacid (5.6 ml) at 0° C. After addition temperature of the reactionmixture was slowly raised to room temperature and then heated to refluxfor 5 h. The reaction mixture was evaporated. Water was added andextracted with ethyl acetate. Ethyl acetate layer was washed withsaturated aqueous sodium bicarbonate, brine, dried and concentratedunder reduced pressure. Crude was purified by column chromatographyusing acetone/hexane (25%) to yield a desired product (2.7 g). ¹H NMR(400 MHz, CDCl₃) d 8.44 (1H, s), 8.30 (1H, d), 7.57 (1H, d), 3.95 (3H,s), 3.78 (3H, s), 3.53 (1H, dd), 3.09-2.93 (3H, m), 2.71 (1H, dd) ppm.

Step 4: Methyl2-oxo-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrole-7-carboxylate

A round bottomed flask was charged with methyl2-(2-methoxy-2-oxo-ethyl)-3-oxo-indane-5-carboxylate (3.0 g, 11 mmol),methanol (60 mL), hydroxyammonium chloride (34 mmol, 2.4 g) and pyridine(46 mmol, 3.7 mL). The resulting yellow solution was refluxed overnight. Water (200 mL) was added and extracted with ethyl acetate (100ml×3). The organic layer was washed with brine, dried (sodium sulphate)and concentrated under reduced pressure to give the corresponding oxime(3.28 g, quant.) and kept crude.To a solution of the crude oxime (3.28 g, 12 mmol) in acetic acid (35mL) at 50-60° C. was added zinc (120 mmol, 7.7 g) portion wise, keepingtemperature below 70° C. After 15 min, zinc was filtered and washed withwater. The filtrate was poured into water and pH was adjusted to 8-9with K₂CO₃. The white suspension was extracted twice with ethyl acetate.The organic phase was washed with HCl 1N giving methyl2-oxo-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrole-7-carboxylate (1.75g, 7.57 mmol, 1.75 g) crude. LC/MS (method B), RT: 0.65 min, ES+232,M+H⁺.

Step 5: Tert-butyl 7-methyl2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1,7-dicarboxylate E3

To a suspension of methyl2-oxo-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrole-7-carboxylate (Step4, 0.75 g, 3.2 mmol) in anhydrous acetonitrile (30 mL) was addeddimethylaminopyridine (0.40 g, 0.32 mmol), triethylamine (2.7 mL, 19mmol) and di-t-butyl dicarbonate (2.8 g, 13 mmol). The solution wasstirred at room temperature overnight. The solution was diluted withethyl acetate and washed with hydrogen chloride (1M) and brine. Thecombined organic layers were dried and concentrated. The residue waspurified by flash chromatography eluting with ethyl acetate andcyclohexane (1/1) to give the title product E3 (990 mg, 92%). LCMS(method B): RT: 0.90 min, ES+685, 2M+Na⁺.

Step 6: Tert-butyl 7-methyl3-(dimethylaminomethylene)-2-oxo-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1,7-dicarboxylateD3

The product was prepare in a similar manner to product D1 (Example 1,step 5) starting from tert-butyl 7-methyl2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1,7-dicarboxylate E3(Example 3, Step 5, 0.500 g, 2.0 mmol) give the title compound D3 (0.610g, quant.). This compound was used without extra purification. LCMS(method B): RT: 0.93 min, ES+387, M+H⁺.

Step 7: Methyl3-(hydroxymethylene)-2-oxo-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-7-carboxylateC3

To a solution of tert-butyl 7-methyl3-(dimethylaminomethylene)-2-oxo-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1,7-dicarboxylate(610 mg, 1.6 mmol) in dioxane (20 mL) was added HCl (36%, 2.9 mL, 32mmol). The solution was stirred overnight at room temperature. Thesolution was diluted with ethyl acetate and washed twice with water,brine, dried over magnesium sulphate and concentrated to give titlecompound (0.300 g, 73%). This compound was used without extrapurification. LC/MS (method B) RT: 0.65 min; ES−: 258, M−H⁺.

Step 8: Diastereoisomer methyl(3E,3aR,8bR)-3-[[(2R)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-2-oxo-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-7-carboxylate(A3) and diastereoisomer methyl(3E,3aR,8bR)-3-[[(2S)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-2-oxo-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-7-carboxylate(B3)

The product was prepare in a similar manner to product A1 and B1(Example 1, step 7) starting from tert-butyl methyl3-(hydroxymethylene)-2-oxo-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-7-carboxylatec3 (Example 3, Step 7, 0.30 g, 1.2 mmol) to give the title compound D3as a mixture of diastereoiomers:

diastereoisomer of methyl(3E,3aR,8bR)-3-[[(2R)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-2-oxo-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-7-carboxylate(A3) (less polar, 73 mg); LCMS (method B) RT 0.78 min; 356 (M+H⁺).

diastereoisomer of methyl(3E,3aR,8bR)-3-[[(2S)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-2-oxo-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-7-carboxylate(B3) (more polar, 54 mg); LCMS (method B) RT 0.78 min; 356 (M+H⁺).

Example 48-cyclopropyl-3-[4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-oneA8 and B8 Step 1:8-cyclopropyl-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one

A 2-necked flask, flushed with argon was charged with (0.35 g, 1.4mmol), 1,2-dimethoxyethane (35 mL, 333 mmol), cyclopropyl boronic acid(0.14 g, 1.7 mmol), tetrakis (triphenylphosphine) palladium (0.16 g,0.14 mmol), water (7 mL) and finally caesium carbonate (1.0 g, 3.1mmol). The resulting mixture was heated to reflux over night. Water wasadded and the solution was extracted with ethyl acetate, washed withbrine and concentrated. The crude material was purified by flashchromatography eluting with ethyl acetate/cyclohexane (99:1) giving8-cyclopropyl-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one (0.17 g,0.7970 mmol, 57%) in mixture with the starting material (77:23). LCMS(method B) RT 0.75 min; 214 (M+H⁺).

Step 2: tert-butyl8-cyclopropyl-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylateE8

To a solution of8-cyclopropyl-3,3a,4,8b-tetrahydro-1H-indeno[1,2-b]pyrrol-2-one (Step 1,0.170 g, 0.79 mmol) in acetonitrile (10 mL, 191 mmol), was addeddi-t-butyl dicarbonate (0.521 g, 2.39 mmol), dimethylaminopyridine(0.097 g, 0.79 mmol) and finally triethylamine (0.673 mL, 4.78 mmol).The mixture was refluxed for an hour. The solution was partitionedbetween ethyl acetate and 1N HCl, extracted, dried and concentrated. Thecrude material was purified by flash chromatography eluting with ethylacetate/cyclohexane (3:17) to give tert-butyl8-cyclopropyl-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylateE8 (0.13 g, 0.41 mmol, 52%) as a yellow oil. LCMS (method B) RT 1.04min; 369, M+H⁺-Boc

Step 3: Tert-butyl(3E)-8-cyclopropyl-3-(dimethylaminomethylene)-2-oxo-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylateD8

The product was prepare in a similar manner to product D1 (Example 1,step 5) starting from tert-butyl8-cyclopropyl-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylateE8 (Example 4, Step 2, 0.13 g, 0.41 mmol) to give the title compound D8(0.16 g, quant.) which was used without further purification in the nextstep. LCMS (method B) RT 1.04 min; ES+759 (2M+Na⁺).

Step 4:(3E)-8-cyclopropyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-oneC8

The product was prepare in a similar manner to product C3 (Example 3,step 7) starting from tert-butyl(3E)-8-cyclopropyl-3-(dimethylaminomethylene)-2-oxo-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylateD8 (Step 3, 0.16 g, 0.43 mmol,) to give(3E)-8-cyclopropyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-oneC8 (0.095 g, 91%) which was used without further purification in thenext step. LCMS (method B) RT: 0.75 min; ES+242 (M+H⁺).

Step 5: Diastereoisomer(3E,3aR,8bS)-8-cyclopropyl-3-[[(2R)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one(A8) and Diastereoisomer(3E,3aR,8bS)-8-cyclopropyl-3-[[(2S)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one(B8)

The product was prepare in a similar manner to product A1 and B1(Example 1, step 7) starting from(3E)-8-cyclopropyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-oneC8 (0.095 g, 0.3937 mmol). Two diastereoisomers were obtained: (A8)(less polar, 25 mg) and (B8) (more polar, 18 mg).

diastereoisomer of(3E,3aR,8bS)-8-cyclopropyl-3-[[(2R)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one(A8) (less polar, 25 mg); LCMS (method B) RT 0.88 min; ES+338 (M+H⁺).

diastereoisomer(3E,3aR,8bS)-8-cyclopropyl-3-[[(2S)-4-methyl-5-oxo-2H-furan-2-yl]oxymethylene]-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one(B8) (more polar, 18 mg); LCMS (method B) RT 0.87 min; ES+338 (M+H⁺).

Example 5 Step 1: tert-butyl2-oxo-5-(3-pyridyl)-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylateE11

Tert-butyl5-bromo-2-oxo-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylate(Example 1. Step 3, 0.500 g, 1.42 mmol), tributyl(3-pyridyl)stannane(0.784 g, 2.12 mmol) and tetrakis(triphenylphosphine) palladium (0.164g, 0.142 mmol) were dissolved in toluene. The mixture was irradiated inthe microwave at 160° C. and normal absorption level for 5 minutes. Thetoluene was removed and the mixture was taken up in acetonitrile andn-hexan. The hexane layer was extracted again with acetonitrile and thecombined acetonitrile layers were dried over sodium sulphate andevaporated. The crude was purified by flash chromatography to givetert-butyl2-oxo-5-(3-pyridyl)-3,3a,4,8b-tetrahydroindeno[1,2-b]pyrrole-1-carboxylateE11 (0.409 g, 82%); LCMS (method A) RT 1.45 min; ES+351 (M+H⁺).The compounds E9-E13 were prepared according to this procedure.

TABLE A Compounds of Formula (I), less polar diastereoisomer (R2 = R3 =R4 = R5 = R7 = R8 = H, R6 = Me, W = O) (I)

LCMS RT Ex. R1 A₁ A₂ A₃ A₄ method (min) Mass A1 H C—H C—H C—H C-allyl C0.88 338, M + H⁺ A2 H C—H C—H C—H C-ethynyl C 0.80 322, M + H⁺ A3 H C—HC—CO₂Me C—H C—H B 0.78 356, M + H⁺ A4 H C—H C—H C—H C—CCMe B 0.85 336,M + H⁺ A5 H C—H C—H C—H C—CCCH₂OMe B 0.81 366, M + H⁺ A6 H C—H C—H C—HC—CCPh B 0.99 398, M + H⁺ A7 H C—H C—H C—H C—CHCH₂ B 0.83 324, M + H⁺ A8H C—CH(CH₂)₂ C—H C—H C—H B 0.88 338, M + H⁺ A9* H C—H C—H C—H C-phenyl C0.90 374, M + H⁺ A10* H C—H C—H C—H C-4-pyridyl A 1.11 375, M + H⁺ A11*H C—H C—H C—H C-3-pyridyl A 1.26 375, M + H⁺ A12* H C—H C—H C—HC-2-thiazolyl C 0.80 381, M + H⁺ A13* H C—H C—H C—H C-2-furyl C 0.86364, M + H⁺ *in diastereoisomeric mixture with the correspondingcompound B.

TABLE B Compounds of Formula (I), more polar diastereoisomer (R2 = R3 =R4 = R5 = R7 = R8 = H, R6 = Me, W = O) (I)

LCMS RT Ex. R1 A₁ A₂ A₃ A₄ method (min) Mass B1 H C—H C—H C—H C-allyl C0.86 338, MH⁺ B2 H C—H C—H C—H C-ethynyl C 0.78 322, MH⁺ B3 H C—HC—CO₂Me C—H C—H B 0.78 356, MH⁺ B4 H C—H C—H C—H C—CCMe B 0.83 336, MH⁺B5 H C—H C—H C—H C—CCCH₂OMe B 0.79 366, MH⁺ B6 H C—H C—H C—H C—CCPh B0.98 398, M + H⁺ B7 H C—H C—H C—H C—CHCH₂ B 0.82 324, M + H⁺ B8 HC—CH(CH₂)₂ C—H C—H C—H B 0.87 338, M + H⁺ B9* H C—H C—H C—H C-phenyl C0.90 374, M + H⁺ B10* H C—H C—H C—H C-2-pyridyl A 1.11 375, M + H⁺ B11*H C—H C—H C—H C-3-pyridyl A 1.26 375, M + H⁺ B12* H C—H C—H C—HC-2-thiazolyl C 0.80 381, M + H⁺ B13* H C—H C—H C—H C-2-furyl C 0.86364, M + H⁺ *in diastereoisomeric mixture with the correspondingcompound A.

TABLE C Compounds of Formula (IIb) (R2 = R3 = R4 = R5 = R8 = H, W = O)(IIb)

LCMS RT Ex. A₁ A₂ A₃ A₄ method (min.) Mass C1 C—H C—H C—H C-allyl C 0.75240, M − H⁺ C2 C—H C—H C—H C—CCSiMe₃ C 0.67 226 M + H⁺ C3 C—H C—CO₂MeC—H C—H B 0.65 258, M − H⁺ C4 C—H C—H C—H C—CCMe B 0.72 240, M + H⁺ C5C—H C—H C—H C—CCCH₂OMe B 0.69 270, M + H⁺ C6 C—H C—H C—H C—CCPh B 0.81325, M − H⁺ C7 C—H C—H C—H C—CHCH₂ B 0.70 228, M + H⁺ C8 C—CH(CH₂)₂ C—HC—H C—H B 0.75 242, M + H⁺ C9 C—H C—H C—H C-phenyl A 1.54 276, M − H⁺C10 C—H C—H C—H C-4-pyridyl C 0.38 277, M − H⁺ C11 C—H C—H C—HC-3-pyridyl C 0.35 277, M − H⁺ C12 C—H C—H C—H C-2-thiazolyl C 0.66 283,M − H⁺ C13 C—H C—H C—H C-2-furyl C 0.73 266, M − H⁺

TABLE D Compounds of Formula (IIb) (R2 = R3 = R4 = R5 = R8 = H, W = O)(IIb)

LCMS RT Ex. A₁ A₂ A₃ A₄ method (min.) Mass D1 C—H C—H C—H C-allyl C 1.05369, M + H⁺ D2 C—H C—H C—H C—CCSiMe₃ C 1.21 425, M + H⁺ D3 C—H C—CO₂MeC—H C—H B 0.93 387, M + H⁺ D4 C—H C—H C—H C—CCMe B 1.04 367, M + H⁺ D5C—H C—H C—H C—CCCH₂OMe B 0.99 397, M + H⁺ D6 C—H C—H C—H C—CCPh B 1.17425, M + H⁺ D7 C—H C—H C—H C—CHCH₂ B 1.01 731, 2M + Na⁺ D8 C—CH(CH₂)₂C—H C—H C—H B 1.04 759, 2M + Na⁺ D9 C—H C—H C—H C-phenyl C 1.06 376, M −H⁺* D10 C—H C—H C—H C-2-pyridyl A 1.34 377, M − H⁺* D11 C—H C—H C—HC-3-pyridyl C 0.80 406, M + H⁺ D12 C—H C—H C—H C-2-thiazolyl C 0.98 412,M +H⁺ D13 C—H C—H C—H C-2-furyl C 1.03 395, M +H⁺ *Product hydrolysisduring the analysis. The mass of the corresponding enol was observed.

TABLE E Compounds of Formula (IIb) (R2 = R3 = R4 = R5 = R8 = H, W = O)(IIb)

LCMS RT Ex. A₁ A₂ A₃ A₄ method (min.) Mass E1 C—H C—H C—H C-allyl B 1.05649, 2M + H⁺ E2 C—H C—H C—H C—CCSiMe₃ C 1.22 761, 2M + H⁺ E3 C—H C—CO₂MeC—H C—H B 0.90 685, 2M + H⁺ E4 C—H C—H C—H C—CCMe C 1.04 645, 2M + H⁺ E5C—H C—H C—H C—CCCH₂OMe C 0.99 705, 2M + H⁺ E6 C—H C—H C—H C—CCPh B 1.18437, M + MeCN + H⁺ E7 C—H C—H C—H C—CHCH₂ B 1.00 621, 2M + Na⁺ E8C—CH(CH₂)₂ C—H C—H C—H C 1.04 649, 2M + H⁺ E9 C—H C—H C—H C-phenyl A1.96 372, M + Na⁺ E10 C—H C—H C—H C-4-pyridyl A 1.32 351, M + H⁺ E11 C—HC—H C—H C-3-pyridyl A 1.45 351, M + H⁺ E12 C—H C—H C—H C-2-thiazolyl A1.80 357, M + H⁺ E13 C—H C—H C—H C-2-furyl A 1.88 362, M + Na⁺

Biological Examples

The effect of compounds of Formula (I) on germination of Orobanchecumana Wallr. seeds was evaluated on glass fiber filter paper (GFFP) inpetri dishes. Seeds were preconditioned at moisture and suitabletemperature to become responsive to the specific chemical germinationstimulants.Test compounds were dissolved in DMSO (10 000 mg l⁻¹) and stored at roomtemperature in a desiccators with desiccants. The stock solutions weredissolved with deionised water to the appropriate final testconcentration.Seeds of O. cumana race ‘F’ were collected from sunflower fields inManzanilla (Seville, Spain) in 2006 (seed lot IN146) and 2008 (seed lotIN153) and stored at room temperature. To separate seeds from heavyorganic debris, a modified sucrose floatation technique as described byHartman & Tanimonure (Plant Disease (1991), 75, p. 494) was applied.Seeds were filled into a separation funnel and stirred in water. Whenseeds floated to the surface, the water fraction containing heavy debriswas discarded. Seeds were re-suspended in 2.5M sucrose solution(specific gravity of 1.20) and heavy debris was allowed to settle downfor 60 min. After removing debris, seeds were disinfected in 1% sodiumhypochlorite solution and 0.025% (v/v) Tween 20 for 2 min. The seedswere decanted onto two layers of cheesecloth, rinsed with steriledeionised water and re-suspended in sterile deionised water. Two ml ofthe seed suspension containing approximately 150-400 seeds were spreadevenly on two layers of sterile glass fiber filter paper disc (Ø9 mm) inPetri dishes (Ø9 cm). After wetting the discs with 3 ml steriledeionised water, petri dishes were sealed with parafilm. Seeds wereincubated for 10 days at 20° C. in the dark for seed conditioning. Theupper disc with conditioned seeds was briefly dried, transferred to apetri dish lined with a dry GFFP disc, and wetted with 6 ml of theappropriate test solution. The compounds of Formula (I) were tested atconcentrations of 0.001, 0.01, and 0.1 mg l⁻¹. The strigolactoneanalogue GR24 (commercially available as a mixture of isomers) wasincluded as positive control and 0.001% DMSO as negative control. Alltreatments were tested in five replicates. Seeds were re-incubated at20° C. in the dark and examined for germination 10 days later. Theradicals of germinated seeds were stained for 5 min with blue ink(MIGROS, Switzerland) in 5% acetic acid according to Long et al. (SeedScience Research (2008), 18, p. 125). After staining, seeds were scannedusing a flatbed scanner with an optical resolution of 1200 dpi (PULSTEK,OpticPro ST28) or photographed using a camera stand mounted with adigital SLR camera (Canon EOS 5D). Germination of 100 seeds perreplicate was evaluated on digital images. Seeds were consideredgerminated when the radical protruded from the seed coat. The results ofthe Orobanche seed germination tests are shown in Tables 3-6.The results show that all compounds tested induced seed germinationcompared to the aqueous control.

TABLE 3 Germination (%) of preconditioned Orobanche cumana seeds of lotIN146, raceF treated with compounds of Formula (I) at differentconcentrations Germination %* at concentration of Compound 0.1 mg l⁻¹0.01 mg l⁻¹ 0.001 mg l⁻¹ A1 82.6 82.0 85.8 A2 86.2 82.0 85.8 *mean; n =5 × 100 seeds; aqueous control (0.001% DMSO) = 0% germination

TABLE 4 Germination (%) of preconditioned Orobanche cumana seeds of lotIN146, raceF treated with compounds of Formula (I) at differentconcentrations Germination %* at concentration of compound 0.1 mg l⁻¹0.01 mg l⁻¹ 0.001 mg l⁻¹ A3 82.6 82.0 85.8 *mean; n = 5 × 100 seeds;aqueous control (0.001% DMSO) = 0% germination

TABLE 5 Germination (%) of preconditioned Orobanche cumana seeds of lotIN153, raceF treated with compounds of Formula (I) at differentconcentrations Germination %* at concentration of compound 0.1 mg l⁻¹0.01 mg l⁻¹ 0.001 mg l⁻¹ A4 98.2 94.4 97.6 A5 99.2 91.4 79.0 GR24 93.896.0 88.6 *mean; n = 5 × 100 seeds; aqueous control (0.001% DMSO) = 0.2%germination

TABLE 6 Germination (%) of preconditioned Orobanche cumana seeds of lotIN153, raceF treated with compounds of Formula (I) at differentconcentrations Germination %* at concentration of compound 0.1 mg l⁻¹0.01 mg l⁻¹ 0.001 mg l⁻¹ A7 95.4 96.8 96.4 GR24 96.8 93.2 79.8 *mean; n= 5 × 100 seeds; aqueous control (0.001% DMSO) = 0.8% germination

TABLE 7 Germination (%) of preconditioned Orobanche cumana seeds of lotIN153, raceF treated with compounds of Formula (I) at differentconcentrations Germination %* at concentration of compound 0.1 mg l⁻¹0.01 mg l⁻¹ 0.001 mg l⁻¹ A6 83.6 40.2 2.6 A8 86.8 88.5 81.2 A9 76.8 84.453.4 A10 24.0 18.0 11.2 A11 90.8 65.6 30.0 A12 26.8 7.0 13.0 A13 90.066.4 13.4 GR24 90.6 83.2 60.8 *mean; n = 5 × 100 seeds; aqueous control(0.001% DMSO) = 0.2% germination

Biological Examples

The effect of compounds of Formula (I) on the germination of Brassicaoleracea cv Botrytis or common cauliflower was tested on tropical types.This type was chosen because it displays different sensitivities tolight conditions and temperature during germination. Germination of asensitive tropical type at 20° is stimulated by the presence of light.Hence, 20° C. in the dark are considered suboptimal or stress conditionsfor germination of this type.The tropical seed batch tested was part of seed batches produced asbasic seed (for maintenance of the parental line) and were processedaccordingly.Germination was assessed using the standard paper germination test forBrassica: Fifty seeds were placed on blue germination paper, which wasmoistened with the appropriate solutions, in closed oblong germinationboxes. Each condition was tested in duplo. Germination boxes were placedin controlled germination cabinets with the appropriate temperature andlight conditions. Germination of seeds was counted at regular intervals.Seeds were considered to be germinated when the radical had protrudedthe testa and endosperm (radical size approximately 1 mm). Germinationkinetics were analyzed using the Germinator analysis tool in order toobtain the parameters: G_(max) (maximum germination) and t₅₀ (timeneeded to reach 50% of the G_(max)). The Germinator analysis tool is anadd-in in for excel developed by the University of Wageningen: Joosen,R. V. L., J. Kodde, et al. (2010). (“Germinator: A Software Package forHigh-Throughput Scoring and Curve Fitting of Arabidopsis SeedGermination.” The Plant Journal 62(1): 148-159.)Test compounds were dissolved in DMSO at a concentration of 50 mM andstored at −20° C. The strigolactone analogue GR24 (commerciallyavailable as a racemic mixture of 2 diastereoisomers, referred to as“synthetic strigolactone GR-24” and first prepared by Johnson A. W. &all, Journal of the Chemical Society, Perkin Transactions 1, 1981, page1734-1743) was included as positive control. Germination solutions wereprepared by diluting the stock solutions with demineralized water till25 μM. As control solutions demineralized water and a 0.05% v/v DMSOsolution were used.The effect of the strigolactone derivatives on germination is shown intable 8. These results show that strigolactones stimulate germination atsuboptimal conditions.

TABLE 8 Germination of seeds of the tropical cauliflower 3C150 (seedbatch 11B295; produced in Chili 2011) in the presence of 25 μM of thedifferent strigolactone derivatives at 20° C. and in the dark. G_(max)^(a) stimulation^(b) compound (%) (%) DMSO 31.3 0.0 GR24 73.0 140.0 A343.0 36.7 ^(a)total germination. ^(b)extra germination compared to theDMSO treatment, expressed as percentage of the DMSO treatment.

1. A compound of Formula (I)

wherein W is O or S; R2 and R3 are independently hydrogen, or C₁-C₃alkyl; R4 and R5 are independently hydrogen, halogen, nitro, cyano,C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, hydroxyl, —OC(O)R9, amine,N—C₁-C₃ alkyl amine, or N,N-di-C₁-C₃ alkyl amine; R9 is hydrogen, C₁-C₆alkyl, C₁-C₆ alkoxy, or C₁-C₆ haloalkyl; R6 and R7 are independentlyhydrogen, C₁-C₃ alkyl, hydroxyl, halogen or C₁-C₃ alkoxy; R8 ishydrogen, nitro, cyano, C₁-C₆ alkyl, C₁-C₆ haloalkyl, halogen, C₁-C₈alkylthio, C₁-C₈ haloalkylthio, C₁-C₈ alkylsulfinyl, N—C₁-C₆ alkylamine, N,N-di-C₁-C₆ alkyl amine, C₁-C₈ haloalkylsulfinyl, C₁-C₈alkylsulfonyl, or C₁-C₈ haloalkylsulfonyl; R1 is hydrogen, C₁-C₆ alkoxy,hydroxyl, amine, N—C₁-C₆ alkyl amine, N,N-di-C₁-C₆ alkyl amine, C₁-C₆alkyl optionally substituted by one to five R10, C₁-C₈ alkylcarbonyl,C₁-C₈ alkoxycarbonyl, aryl optionally substituted by one to five R10,heteroaryl optionally substituted by one to five R10, heterocyclyloptionally substituted by one to five R10, or benzyl optionallysubstituted by one to five R10; R10 is hydrogen, cyano, nitro, halogen,C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, or C₂-C₆alkynyl; A₁, A₂, A₃ and A₄ are each independently C—X, C—Y or nitrogen,wherein each X or Y may be the same or different, and provided that nomore than two of A₁, A₂, A₃ and A₄ are nitrogen and that at least one ofA₁, A₂, A₃ and A₄ is C—X; Y is hydrogen, halogen, cyano, hydroxyl,—OC(O)R9, C₁-C₆ alkoxy, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₃hydroxyalkyl, nitro, amine, N—C₁-C₆ alkyl amine, N,N-di-C₁-C₆ alkylamine, or NHC(O)R9; X is C₂-C₈ alkenyl optionally substituted by one tofive R11, C₂-C₈ alkynyl optionally substituted by one to five R11, C₃-C₇cycloalkyl, C₃-C₁₀ cycloalkyl substituted by one to five R12,C₁-C₈alkylcarbonyl, C₁-C₈ alkoxycarbonyl, N—C₁-C₆ alkyl aminocarbonyl,N,N-di-C₁-C₆ alkyl aminocarbonyl, aryl optionally substituted by one tofive R13, or heteroaryl optionally substituted by one to five R13; eachR11 is independently halogen, cyano, nitro, hydroxy, C₁-C₈ haloalkyl,C₁-C₈alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ alkylthio, C₁-C₈ haloalkylthio,C₁-C₈ alkylsulfinyl, N—C₁-C₆ alkyl amine, N,N-di-C₁-C₆ alkyl amine,C₁-C₈ haloalkylsulfinyl, C₁-C₈ alkylsulfonyl, C₁-C₈ haloalkylsulfonyl,C₁-C₈alkylcarbonyl, C₁-C₈ alkoxycarbonyl; or aryl optionally substitutedby one to five halogen, C₁-C₃ alkyl, C₁-C₃ alkoxy; or heteroaryloptionally substituted by one to five halogen, C₁-C₃ alkyl, C₁-C₃alkoxy; each R12 and R13 are independently halogen, cyano, nitro,hydroxy, C₁-C₈ alkyl, C₁-C₈alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ alkylthio,C₁-C₈ haloalkylthio, C₁-C₈ alkylsulfinyl, N—C₁-C₆ alkyl amine,N,N-di-C₁-C₆ alkyl amine, C₁-C₈ haloalkylsulfinyl, C₁-C₈ alkylsulfonyl,C₁-C₈haloalkylsulfonyl, C₁-C₈alkylcarbonyl, C₁-C₈ alkoxycarbonyl, orphenyl; or salts or N-oxides thereof.
 2. A compound according to claim1, wherein W is O.
 3. A compound according to claim 1 or 2, wherein: R2and R3 are independently hydrogen, methyl, or ethyl; R4 and R5 areindependently hydrogen, hydroxyl, methyl or ethyl; R6, R7 and R8 areindependently hydrogen, methyl or ethyl; R1 is hydrogen, C₁-C₆ alkoxy,C₁-C₆ alkyl optionally substituted by one to five R10, C₁-C₈alkylcarbonyl, C₁-C₈ alkoxycarbonyl, aryl optionally substituted by oneto five R10, heteroaryl optionally substituted by one to five R10,heterocyclyl optionally substituted by one to five R10, or benzyloptionally substituted by one to five R10; R10 is independentlyhydrogen, cyano, nitro, halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₁-C₆haloalkyl; A₁, A₂, A₃ and A₄ are each independently C—X or C—Y andprovided that at least one of A₁, A₂, A₃ and A₄ is C—X; Y is hydrogen,hydroxyl, halogen, cyano, methyl, hydroxymethyl, trifluoromethyl ormethoxy; X is vinyl, 1-propenyl, allyl, propargyl, cyclopropane,cyclobutane, cyclopentane, ethynyl, benzene ethynyl, methyl ethynyl,phenyl optionally substituted by one to five R13, pyridyl optionallysubstituted by one to five R13, furanyl optionally substituted by one tofive R13, thiophenyl optionally substituted by one to five R13, thiazoyloptionally substituted by one to five R13, methoxycarbonyl,hydroxycarbonyl, methylaminocarbonyl, or dimethylaminocarbonyl; and R13is halogen, cyano, nitro, hydroxy, methoxy, or methyl.
 4. A compoundaccording to claim 1, wherein X is vinyl, 1-propenyl, allyl, propargyl,cyclopropane, ethynyl, phenyl, pyridyl, furanyl, thiophenyl, thiazoyl,methoxycarbonyl, hydroxycarbonyl, methylaminocarbonyl, ordimethylaminocarbonyl.
 5. A plant growth regulator or seed germinationpromoting composition, comprising a compound according to claim 1, andan agriculturally acceptable formulation adjuvant.
 6. A method forregulating the growth of plants at a locus, wherein the method comprisesapplying to the locus a plant growth regulating amount of the compoundaccording to claim
 1. 7. A method for promoting the germination of seedscomprising applying to the seeds, or a locus containing seeds, a seedgermination promoting amount of the compound according to claim
 1. 8.The method according to claim 7 wherein the plant of the seed is a plantselected from the genus brassica.
 9. A method for controlling weedscomprising applying to a locus containing weed seeds a seed germinationpromoting amount of the compound according to claim 1, allowing theseeds to germinate, and then applying to the locus a post-emergenceherbicide.
 10. (canceled)
 11. A compound of Formula (II)

wherein W is O or S; R2 and R3 are independently hydrogen, or C₁-C₃alkyl; R4 and R5 are independently hydrogen, halogen, nitro, cyano,C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, hydroxyl, —OC(O)R9, amine,N—C₁-C₃ alkyl amine, or N,N-di-C₁-C₃ alkyl amine; R9 is hydrogen, C₁-C₆alkyl, C₁-C₆ alkoxy, or C₁-C₆ haloalkyl; R8 is hydrogen, nitro, cyano,C₁-C₆ alkyl, C₁-C₆ haloalkyl, halogen, C₁-C₈ alkylthio, C₁-C₈haloalkylthio, C₁-C₈ alkylsulfinyl, N—C₁-C₆ alkyl amine, N,N-di-C₁-C₆alkyl amine, C₁-C₈ haloalkylsulfinyl, C₁-C₈ alkylsulfonyl, or C₁-C₈haloalkylsulfonyl; R1 is hydrogen, C₁-C₆ alkoxy, hydroxyl, amine,N—C₁-C₆ alkyl amine, N,N-di-C₁-C₆ alkyl amine, C₁-C₆ alkyl optionallysubstituted by one to five R10, C₁-C₈ alkylcarbonyl, C₁-C₈alkoxycarbonyl, aryl optionally substituted by one to five R10,heteroaryl optionally substituted by one to five R10, or benzyloptionally substituted by one to five R10; R10 is hydrogen, cyano,nitro, halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkyl, C₂-C₆alkenyl, or C₂-C₆ alkynyl; A₁, A₂, A₃ and A₄ are each independently C—X,C—Y or nitrogen, wherein each X or Y may be the same or different, andprovided that no more than two of A₁, A₂, A₃ and A₄ are nitrogen andthat at least one of A₁, A₂, A₃ and A₄ is C—X; Y is hydrogen, halogen,cyano, hydroxyl, —OC(O)R9, C₁-C₆ alkoxy, C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₁-C₃ hydroxyalkyl, nitro, amine, N—C₁-C₆ alkyl amine, N,N-di-C₁-C₆alkyl amine, or NHC(O)R9; X is C₂-C₈ alkenyl optionally substituted byone to five R11, C₂-C₈ alkynyl optionally substituted by one to fiveR11, C₃-C₇ cycloalkyl, C₃-C₁₀ cycloalkyl substituted by one to five R12,C₁-C₈alkylcarbonyl, C₁-C₈ alkoxycarbonyl, N—C₁-C₆ alkyl aminocarbonyl,N,N-di-C₁-C₆ alkyl aminocarbonyl, aryl optionally substituted by one tofive R13, or heteroaryl optionally substituted by one to five R13; eachR11 is independently halogen, cyano, nitro, hydroxy, C₁-C₈ haloalkyl,C₁-C₈alkoxy-, C₁-C₈ haloalkoxy, C₁-C₈ alkylthio, C₁-C₈ haloalkylthio,C₁-C₈ alkylsulfinyl, N—C₁-C₆ alkyl amine, N,N-di-C₁-C₆ alkyl amine,C₁-C₈ haloalkylsulfinyl, C₁-C₈ alkylsulfonyl, C₁-C₈ haloalkylsulfonyl,C₁-C₈alkylcarbonyl, C₁-C₈ alkoxycarbonyl; or aryl optionally substitutedby one to five halogen, C1-C3 alkyl, C1-C3 alkoxy; or heteroaryloptionally substituted by one to five halogen, C1-C3 alkyl, C1-C3alkoxy; and each R12 and R13 are independently halogen, cyano, nitro,hydroxy, C₁-C₈ alkyl-, C₁-C₈ alkoxy-, C₁-C₈ haloalkoxy, C₁-C₈ alkylthio,C₁-C₈ haloalkylthio, C₁-C₈ alkylsulfinyl, N—C₁-C₆ alkyl amine,N,N-di-C₁-C₆ alkyl amine, C₁-C₈ haloalkylsulfinyl, C₁-C₈ alkylsulfonyl,C₁-C₈ haloalkylsulfonyl, C₁-C₈alkylcarbonyl, C₁-C₈ alkoxycarbonyl, orphenyl; or salts or N-oxides thereof.
 12. A method of enhancing cropplants by applying to the plants, plant parts, plant propagationmaterial, or a plant growing locus, a compound according to claim
 1. 13.A method according to claim 12 for improving plant yield, comprisingapplying to a plant, plant part, plant propagation material, or a plantgrowing locus, a compound according to claim
 1. 14. A method accordingto claim 12 for improving plant input use efficiency, comprisingapplying to a plant, plant part, plant propagation material, or a plantgrowing locus, a compound according to claim
 1. 15. A method accordingto claim 12 for improving plant vigour and/or plant quality, and/orplant tolerance to stress factors, comprising applying to a plant, plantpart, plant propagation material, or a plant growing locus, a compoundaccording to claim 1.